DE2234819A1 - PROCESS FOR THE MANUFACTURING OF AGRICULTURAL USE OF SLOW-RELEASE NITROGEN - Google Patents

Description

Dr. Hans-Heinrich Willrath

Dr. Dieter Weber
Dipl.-Phys. Klaus Seiffert

PATENT LAWYERS

D - 62 WIESBWFH, July 10, PO Box 1327 3 Gustav-Freytag-Straße & (06121) 372720 1 / (J ^ Telegram address: WlLLmTENT

File 5100-744

Allied Chemical Corporation Morristown, New Jersey 07960 UNITED STATES.

Process for the production of nitrogen that can be used in agriculture slow-release products

Priority ; from July 16, 1971 in USA,

Ser.-No. 163 305

dated February 22, 1972 "I _n " USA, Ser.-No. 228 313

from February 4, 1972 in USA, Ser.-No. 223 696

of March 13, 1972 in USA, Ser.-No. 234 415

from April 18, 1972 in USA, Ser.-No. 245 269

Farm animals are usually divided into two classes, ruminants and monogastric animals. Ruminant, which includes horned cattle and sheep, have a complicated stomach made up of several compartments, the one closest to the reticulum Stomach is known as rumen or rumen. ruminant

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Frankfurt / Main 6763 Bank: Dresdner Bank AG, Wiesbaden, account no. 276

2234813

are known to have the special ability to use non-proteinaceous nitrogen compounds such as urea, biuret, formamide and acetamide as well as phosphorus and sulfur compounds such as ammonium phosphate and ammonium sulfate, this will achieved through the symbiosis relationship between microorganisms that multiply in the rumen and reticulum of ruminants, which actually take advantage of the compounds and convert them into organic material, which in turn is digested and used by ruminants can be absorbed.

As a non-protein source of nitrogen, urea is special meaningful for feeding ruminants because it is a concentrated and economical form of nitrogen represents. Pure nitrogen contains around 46.5% nitrogen, but the amount that is certainly found in ruminant feed can be introduced is limited by the fact that it has a certain limit of toxicity to ruminants. As a result, the art has long sought a practical and economical way to convert urea into Recycle animal feed while minimizing toxic properties.

The USA patent specification 3 490 912 describes the mixing of a urea solution with a solid absorbent feed, Drying the mixture and pelletizing the dried feed containing urea. Such urea-containing feed, as they are currently used in animal feed, but unfortunately must be given in limited quantities, because if

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Containing too much in the feed or the urea not good mixed with the other ingredients, digestive or other disturbances that can even lead to death.

The object of the invention is to create a method for Conversion of cheap carbohydrate materials containing polysaccharides into valuable nitrogen which is slowly releasing Composition useful in agriculture and the synthetic nitrogen is safe and effective in agricultural environment without the addition of undesirable for the environment Materials. The process is therefore intended to improve the nutrition of ruminants, and it is important to that the ruminant feed is in a pelletized form accrues, the pellets having improved breaking strength. At the same time it is used for the production of the pelletized ruminant feed valuable that the pelletization rate is increased significantly. The nitrogen should on the other hand are released slowly and regulated in the room, so that it can be safely and effectively used by the livestock.

In the general sense, the invention relates to a method for Preparation of a slowly releasing nitrogen composition, which is suitable for use as a protein substitute in ruminant feed and as a fertilizer for plant growth; the method according to the invention comprises the following steps?

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a) Soak a solid carbohydrate material, the water-insoluble one Contains polysaccharides, with an aqueous solution of an amide, such as urea, biuret, formamide or acetamide and one acid catalyst which is non-toxic to ruminants and which hydrolyses the polysaccharides to form with the Amide-reactive carbony groups catalyzed,

b) The soaked solid material is dried at a temperature in the range of 71 to 143 ° C (160 to 290 ° F) and formed into a dry nitrogen slowly releasing product implemented, the amide-polysaccharide adducts and at least about 5% Contains water and

c) this product is cooled to ambient temperature.

Another embodiment of the invention relates to a method to produce a pelletize nitrogen slowly releasing mass used as a protein substitute in ruminant feed and as a fertilizer for growing plants suitable is; this process comprises the following stages:

a) A solid carbohydrate material containing water-soluble polysaccharides is soaked with an aqueous solution of a Amides, such as urea, biuret, formamide or acetamide and an acidic catalyst, which is preferably composed of sulfuric acid, phosphoric acid or acidic ammonium salts of sulfuric acid and phosphoric acid and used to hydrolyze the polysaccharides Formation of reactive carbonyl groups with the amide is used.

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b) This impregnated solid material is dried at a temperature in the range of 71 to 143 ° C (160 to 290 ° F) and converted into a dry intermediate, the amide-polysaccharide adducts and contains at least 5% water.

c) This intermediate product is pelletized and agglomerated while maintaining its temperature at at least about 60 ° C and

d) the pelletized product is cooled to ambient temperature.

In yet another embodiment, the dried intermediate product from step b) is prior to pelletization and Agglomeration with a concentrated aqueous urea formaldehyde solution of 60 to 90% total solids and about 0.5 to 6.5 moles of formaldehyde per mole of urea coated. This results in improved agglomeration of the intermediate product . The pelletized product of the invention normally has a total nitrogen content of about 2 up to 10% with a water-insoluble nitrogen content of about 50 to 90% of the total nitrogen. The nitrogen can either determined as soluble or insoluble nitrogen by AOAC tests (AOAC Official Methods of Analyzes, 11th Edition, 1970, p. 18).

Expressed as ruminant nutrients contains the pelletized Product preferably about 50 to 60% protein equivalent. That

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"" fi "·

Protein equivalent of the product can be regulated by adjusting the proportion of the amide solution that you get with the solid Carbohydrate material mixed.

Suitable acidic catalysts for use in the process are sulfuric acid, acidic ammonium sulfate, ammonium sulfate orthophosphoric acid, Pyrophosphoric acid, superphosphoric acid and acidic ammonium salts of these phosphoric acids. AIa catalysts Preferred are superphosphoric acid and ammoniated superphosphoric acid, which are made from wet process phosphoric acid is because these materials provide valuable nutritional phosphates, are readily available commercially, and normally Contain soluble trace minerals necessary for the nutrition of plants and animals.

Aqueous ammoniated phosphoric acid for use in the process of the invention can be prepared by using aqueous Wet process phosphoric acid evaporates to form superphosphoric acid, which is then ammonisiefct. The Canadian patent specification 812 689 of the applicant relates to the concentration of wet process phosphoric acid for the production of superphosphoric acid, d. H. Phosphoric acid containing polyphosphates.

The preferred aqueous ammoniated superphosphoric acid according to the invention has a pH of about 5 to 6, suitably about 6, a nitrogen content of about 9 to 12% by weight, preferably about 10 to 11%, a total phosphoric acid content measured as Po ⁰ S ^{of about 28} to 39 wt%, preferably about

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34 to 38%, including polymeric phosphate on about 30 to 70% by weight, preferably about 55 to 65% by weight, based on based on the weight of the total phosphorus content. To the polymeric phosphates include pyrophosphates and polyphosphates.

An aqueous ammoniated superphosphoric acid, hereinafter referred to as "Solution A", was found to be particularly useful for the purposes of the invention:

Wt%

Nitrogen 10.1

Phosphorus (as Σ ^ δ * 34.2 Trace minerals 1 to 2

Iron (Fe-O ₃ J about 1.0

Calcium (CaO) about 0.1

Magnesium (MgO) about 0.3

pH 6.0

specific weight at 15.6 ° C

(60 ° F) 1.4

Salting out temperature around -18 ° C (O ⁰ F)

The weight distribution of the ammonium phosphates in solution A was about

35% ammonium orthophosphate
51% ammonium pyrophosphate

8% ammonium tripolyphosphate
5% ammonium tetrapolyphosphate
1% higher ammonium phosphates

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* - ft -

If you have a concentrated aqueous urea formaldehyde solution used in carrying out the method of the invention, any suitable urinary formaldehyde solution is the desired concentrations of compounds useful. From a practical point of view, however, it is advantageous to To use urea-formaldehyde solutions in which the form »aidehyd component in the form of stabilized urea-formaldehyde reaction products is spent as they are according to the teachings of the ÜSA patents 2,652,377 of September 15, 1953 and 3,462,256 dated August 19, 1969. A preferred solution made in accordance with U.S. Patent 2,652,377 contains about 10 to 15% water and about 80 to 85% urea formaldehyde solids, the molar ratio of formaldehyde to urea being between about 4.2 and 5.2.

A durable urea-formaldehyde solution, hereinafter referred to as a solution B, having the following properties was found to be particularly useful for the purposes of the invention. Solution B is a clear, colorless, viscous, stabilized solution of formaldehyde and urea reaction products in a small one Amount of water. It contains about 15% water and about 85% solids, the latter being in a molar ratio of formaldehyde bound to urea by about 4.6 to 1. Presumably, the formaldehyde is at least partly in the form of Polymethyllolureas.

According to a preferred embodiment, the method using either superphosphoric acid or ammonium

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Sated superphosphoric acid can be carried out. The expediency However, for the sake of the preferred mode of operation of the invention, expressed below as the incorporation of a liquid supplement, the mainly ammoniated superphosphoric acid, Containing urea, ammonium sulfate and water, in a relatively non-adsorbent feed material, such as fresh or sun-treated alfafa grass or corn. The mixture obtained is converted in a rotary dryer at temperatures and dwell times and dewatered, which is exactly . to be regulated in such a way that most water, however, is not so it is ensured that the valuable natural amino acids, Vitamins and other growth factors are destroyed. It is advisable to use a small proportion of water-soluble polysaccharides, like molasses, added as a concentrated carbonyl source for setting. The partially dried Supplemented feed materials are then pelletized. It has been found to be approximately uniform in value Feed product made from nutritionally fluctuating natural feed materials to brew grain, protein and minerals in an economically advantageous form th.

The most favorable conditions for the production of ruminant feed with a high and constant nutritional value are as follows:

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condition

Supplementary mass

airanized superphosphoric acid (dry substance)

Ammonium sulfate

Molasses (or other water-soluble polysaccharides)

urea

natural feed base

(containing water-soluble and water-insoluble Polysaccharides)

Relationship between natural base and supplement

Drying temperature

(actual temperature of the solids) residence time in the dryer Water content of the natural feed Water content of the finished product Pelletizing temperature

Hold time before the pellets cool down

preferred

15-25% by weight 4-8% by weight

0-20% by weight 20-30% by weight

, Alfalfa, corn plants

6-10 parts per part

82-115 ° C (180-240 ° F)

5-6 minutes - 75% by weight 6-12% by weight

- 150 ° e (140 - 300 ⁰ F)

1-60 minutes

JQs grain feed is suitable for green corn, which is preferred in the early tooth corn stage is cut.

It is generally accepted that high protein nitrogen, such as urea, best in conjunction with protein nitrogen for best results is used in ruminant feed. According to the invention, however, the ratio of urea to natural protein can if desired because a considerable proportion of the urea in the slowly released nitrogen is

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is converted * which is not valid for ruminants. Although, As mentioned, corn feed or alfalfa is the preferred feed is can also be absorbent in the invention with advantage Feed materials are used, the following oils list other suitable feed materials along with their protein value:

Name nominal protein value

8th , 66 10 , 83 7th , 78 6th , 68

dried beet pulp
dried molasses beet pulp
dried potato schnitzel
dried citrus schnitzel

According to a preferred embodiment of the invention an aqueous additive containing 15 to 25% by weight of ammoniated superphosphoric acid (dry matter), 4 to 8% ammonium sulfate, 0 to 20% molasses or other water-soluble polysaccharides and 20 to 30% urea on chopped or ground sun dried alfalfa in a suitable one Plant, e.g. B. a hard mixer circulated or mixed. Alfalfa grass and supplement solution are preferably used when sufficient high temperature mixed to the urea during of the spraying and mixing process in an aqueous solution. Usually a temperature range of 10 to 38 ° C is used (50 to 100 ° F) depending on the concentration of the supplement solution used. The spraying process continues until the mass is up 60% by weight protein equivalent based on dry matter,

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holds. The moist mass is dried at a temperature of about 82 to 116 ⁰ C (180 to 240 ° F). A gas-fired dryer is expediently used for drying. The temperature of the product in the dryer to go out niht above about 143 C (290 ° F) and is normally maintained in the range of 82 to 116 ° C (180 to 240 ⁰ F). If the drying temperature is too high, some of the protein in the alfalfa can decompose. The soaked grass is dried sufficiently for 5 to 60 minutes to remove the main amount of water, but not to the extent that valuable natural amino acids, vitamins and other growth factors are destroyed, ie the material is brought to a dry, free-eating state with water at a level of brought no less than about 6% and no more than about 12%. During drying, a considerable proportion of the urea reacts with partially hydrolyzed polysaccharides to form polysaccharide-urea adducts.

The so prepared and dried soaked alfalfa grass can be blended with water-soluble polysaccharides or other natural ruminant feed? * the water-soluble polysaccharides are generally added before drying. The dried soaked alfalfa grass is made preferably pelletized at a temperature in the range of about 93 to 150 ° C (200 to 300 ° F) with the remainder being urea becomes more soluble in the water retained by the dried soaked absorbent «The liquid phase of the material to be pelletized rises to at least

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about 16 6% by weight of the dried soaked absorbent / which allows an increased pelletizing rate. Another Implementation of urea with hydrolyzed polysaccharides occurs during the pelletizing process at temperatures of

z. B. 60 to 150 ° C (140 to 300 ⁰ F) and pressures from 35 to

1,400 kg / cm (500 to 20,000 psig). While keeping the temperature keeps at 60 to 150 ° C, the ruminant feed mixture pressed through a mouthpiece to form a strand and broken up into pellets. The amount of supplement in the overall batch varies with need for protein supplementation and can range from about 9 to 14% or more of the total diet. That Pelletized feed mix is preferably at ambient temperature within about 1 to 60 minutes after pelletization cooled down. To a certain extent, the reaction of residual urea with polysaccharides continues after pelletization until the product has cooled. Pelletization can be carried out by any conventional method, including the known hard pelletizers are used, and one can use pellets of different sizes according to your needs. In general pellets ranging in size from about 1.5 to 25 mm (1/16 to 1 inch) in diameter are used.

The following examples serve to further explain the Invention. The percentages relate to weight. Solutions A and B used in these examples were described above.

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example 1

This example explains the production of horned cattle feed with a consistently high nutritional value from alfalfa grass with variable nutritional quality. The alfalfa grass was harvested from several Nebraska fields in the summer and early fall and dried in the sun before being transported to the feed production facility. The grass was harvested from high-yield and relatively low-yield fields and at different times in the mowing cycle. Grass harvested from high yield fields and late in the mowing cycle had lower nutritional value than grass harvested under more favorable conditions. The sun-dried grass from plots with different nutritional values was transported to the forage facility for conversion into uniform ruminant forage suitable for use as the main ingredient in starter and horned cattle rations.

The grass received from the forage facility was chopped, not suitable material has been removed. The composition of a typical Alfaifaheu sample was as follows:

Component percent

Protein 15.1

Humidity 25.9

Fat (ether extract) 2.9

Crude fiber (polysaccharides) 16.3

Ashes 8.3

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The mineral content of the alfalfa hay was as follows:

Component percent

Phosphorus 0.23

Potassium 2.10

Sulfur 0.10

Calcium 1.25

Magnesium 0.31

Sodium 0.07

Iron 0.04

Chloride '0.46

as well as smaller amounts of manganese, zinc, cobalt, copper and iodine.

The following amino acids were also in the supplied AIfalfa hay available:

Component percent

Threonine 0.8

Tryptophan 0.4

Methionine 0.2

Lysine 0.9

Arginine 0.7

Glycine ° / ⁹ -

Histidine 0.4

Isoleucine 0.7

Leucine 1.3

Phenylalanine 0.7

Tyrosine 0.3

Alanine 0.8

Aspartic Acid 1 * 9

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Component percent

Glutamic acid 1.8

Proline 0.6

Serine 0.6

Valine 0.8

Liquid replenishment was carried out by admixing the following Components practically in the conditions of the environment with the formation of a free-flowing, fairly clear solution

solution from the following components:

Component percent in the mixture

Solution A 30.0

Ammonium sulfate crystals 6.8

Sugar cane molasses 10.0

65% aqueous urea solution 39.5

Water (total moisture 44.5%) 13.7

100.0

Solution A, described in more detail above, is an aqueous ammoniated superphosphoric acid with 10.1% N and 34.2% phosphate as PO _5, produced by ammonizing superphosphoric acid from wet process phosphoric acid. Of the phosphate present, 65% was in the polyphosphate form and 35% in the orthophosphate form.

The liquid feed supplement contained 100% protein equivalent and was composed as follows:

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Component percent

Nitrogen 16.4

Protein equivalent 100.0

Phosphorus. 4.4

Sulfur 2.0

There were also considerable amounts of iron, aluminum, calcium and magnesium.

The chopped grass was put in a conventional mixer, and the make-up liquid was also put in the mixer brought in. The feed line was started at a rate of about 3 t / h alfalfa and 318 kg / h (700 pounds / h) liquid feed additive to the mixer. The rate of feed supplementation fluctuated as needed to provide a protein equivalent of around 26-28% in the finished product, estimated by nitrogen content, keep upright. Product samples were drawn every 5 minutes and analyzed to ensure consistency of results to ensure. The analyzes performed on certain samples gave the following percentages by weight Protein equivalent, phosphorus, sulfur and moisture after the respective time periods.

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protein phosphorus sulfur 2234819 Time 28.3 o, 72 0.29 humidity 5 min 26.4 0.74 0.30 8.0 25 min 27.1 0.71 0.32 8.1 75 min 27.1 0.69 0.32 8.4 100 min 26.3 0.71 0.31 8.6 120 min Mean value 27> 0 0.72 0.31 8.6 8.3

The moist, soaked Alfaifa product formed in the mixer was fed to a conventional gas-fired rotary dryer. Natural gas was burned with air, and the combustion gases were fed to the dryer. This was appropriately controlled to give a temperature of the dry product of about 82 ° C (180 ⁰ F), and the resulting product contained about 8% of water. The residence time in the dryer was about 7 minutes. The dried soaked hay and heating exhaust gases were blown with air from the dryer into a conventional cyclone separator, where the exhaust gases and fines were separated from one another. The remaining dried soaked hay was then blown with air into the feed hopper of a pelletizing machine. 5 mm (3/8 inch) consisted. The pelletizing temperature in the mouthpiece was about 63 ⁰ C (145 F). The product pelletized at this temperature was fed to a conventional cooler, where the pellets were cooled to ambient temperature within 1 to 4 minutes, whereupon they

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were taken into stock.

The make-up fluid was used during a test period of 120 minutes. The total weight of sun dried hay in the system during the test period of Minutes was 5,355 kg (11,804 pounds). The amount of feed supplement used during this period was 633 kg (1,396 pounds). The amount of collected during those 120 minutes pelletized ruminant feed supplement 5,114 kg (11,275 pounds). A small amount of dust and fines was carried out of the system, however, meant no significant portion of the product. The recovery of protein equivalent by the process was 95.8%. Analyzes of several of the essential amino acids were run on the product pellets to ensure that none Degradation had occurred in the proceedings. The results were as follows:

Component %

Threonine 0.8

Methionine 0.2

Lysine 0.9

Aspartic acid 1.9

The product pellets were also based on certain metals with the following Results analyzed:

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Components%

Potassium 2.00

Calcium 1.20

Magnesium 0.28

Sodium 0.07

Elsen 0.06

Chloride 0.40

By selecting pellets about 13 mm in length, they were tested for crush strength. The diameter of all of the Sprout-WaldJEon machine pressed pellets was 9.5 mm. The crush strength of the pellets was measured by placing a pellet on an aluminum plate on a balance and applied pressure to it with a smooth flat aluminum plate, until the pellet broke. The pressure exerted on the balance at the moment it tore was recorded. Of the Pressure was directed perpendicular to the pellet diameter. Pellets just before initiating the addition of the supplement and 5 minutes after the addition of the supplement was stopped were included in the evaluations. Mean values for 10 pellets from each sample were as follows:

Weight required for the sample

for crushing

5 minutes before the start of the addition, 5 minutes after the start of the addition 25 minutes after the start of the addition, 75 minutes after the start of the addition, 100 minutes after the start of the addition

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kg lb 32 71 70.3 155 69.9 154 68.5 151 68.5 151

12O min after the start of the addition 64, O 141 5 min after the addition was stopped 38.1 84

The increase in pellet strength noted above from the addition of the supplement was accompanied by one Decrease in dust formation and tendency to chafing at the point where the pellet is cut by the pelletizer became.

Example 2

After completion of the 2-hour experiment of Example 1 was the inflow of the supplementary liquid stopped and the system operated for 1 hour without supplementary liquid to the Exhausting hay feed. Then the feeding of the system was started by a new supply of hay, which was towards the end of the growing season was produced under conditions of only moderate productivity. The new batch of AIfalfa grass was added to the feed line and the chopper tilted in and the system continued to operate without being switched off.

The analysis of the alfalfa hay intake in this example was as follows: Component %

protein 11.3 humidity 29.8 Fat (ether extract) 1.7 Crude fiber (polysaccharides) 19.9

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Ashes 6.3

Phosphorus 0.17

Potassium 2.00

Sulfur 0.08

Calcium 1.20

Magnesium, 0.30

Sodium 0.07

Iron 0.03

Chloride 0.50

Small amounts of manganese, zinc, cobalt, copper and iodine were also present. The hay in this example contains the same Amino acids such as the hypocritical charge used in Example 1 but in lower concentrations. Since the hay in this example is only about 79% as much protein on dry matter as Containing the hay of Example 1, the amount of additive used was increased accordingly to increase the nutritional value of the feed hold constant by increasing the supplement feed rate to about 404 kg / h (890 pounds / h). The supplement had the same Eusara setting as in example 1. The The feed rate of the hay remained at around 3 t / h. Working conditions were controlled as in Example 1. Product samples were drawn at 5 minute intervals to ensure uniformity of the results. In the test, which lasted 120 minutes, the sample analyzes in% by weight gave the following values of protein equivalent phosphorus, sulfur and moisture at the respective point in time:

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protein phosphorus sulfur 223481S Time 26.9 0.70 0.30 humidity 5 min 27.9 0.70 0.38 8.8 25 min 28.0 0.73 0.36 8.6 75 min 28.1 0.74 0.38 8.7 100 min 27.5 0.72 0.37 8.8 120 min 27.7 0.72 0.36 8.4 Average 8.6

In this example, the amount of sun dried hay placed in the system during the 120 minute test period was 5,398 kg (11,900 pounds). The amount of nutrient supplement concentrate used during this test period was 804 kg (1,773 pounds). The amount of the pelleted supplement containing ruminant feed collected was 5,222 kg (11,511 pounds). The recovery of protein equivalent throughout the process was about 100%. The firmness of the pellets was on average somewhat greater than that of the pelletized product of Example 1. Comparing the overall results from Examples 1 and 2, a solid pelletized putter product with constant nutritional value was produced, the protein value of which was 27.0 to 27.7 % was maintained when the protein content of the raw feed material _{decreased from 1.5 r} l to 11.3%. Pellet strength increased with the addition of the supplement.

Example 3

This example shows the addition of the whole corn plant

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a nutritionally acceptable feed suitable for use as the main part of a horned cattle ration, with a supplement liquid containing suspended solids is used. The overall procedure was carried out essentially as described in Example 1. Most of the plants were Harvested in the early tooth stage and consisted of about 50% yellow corn, 25% stalks, 12% leaves, 10% cobs and 5% pods.

The whole corn plants were brought from the field to the forage facility and went through the feed inlet and chopper, where the corn plants were reduced to particles of workable size and waste material has been removed. The analysis of the corn plant was as follows:

Component %

Humidity 65.0

Protein 2.5

Fat ■ 0.8

Ashes If5

Phosphorus 0.7

Calcium 0.2

Sugars (mainly polysaccharides) 1.6

Carbohydrates (polysaccharides) 22.3

The feed supplement liquid used was made by mixing the following ingredients:

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in the mixture 2234819 Component % 30.0 Solution a 10.0 Ammonium sulfate crystals 40.0 aqueous urea solution
(65% urea) 5.0 CaCO ₃ (powdered limestone) 15.0 Water (total moisture 42.0%)

100.0

Since the supplement contained some suspended solids, it was agitated to prevent them from settling. The supplementary liquid contained 106% protein equivalent and was like is composed as follows:

Component %

Nitrogen 17.1

Protein equivalent 106.0 phosphorus 4.6

Sulfur 2.5

Calcium 2.0

The plant was started at a rate of about 5 t / h of chopped whole corn plants and about 454 kg (IOOO pounds / hr) feed supplement liquid. These RAs became as constant as possible during the 2-hour test period held. Product samples were taken at 5 minute intervals to ensure operation was continued throughout Attempt was constant. The analyzes carried out on the samples gave the following values in% by weight at the respective point in time *}

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-2 B-

protein phosphorus humidity 2234819 Time 28.8 2.4 8.4 5 min 28.6 2.6 8.1 25 min 29.1 2.5 8.5 75 rain 29.8 2.2 8.7 100 min 29.2 2.7 8.7 120 min Mean 29.1 2.5 8.5

The introduction of combustion gases into the dryer resulted in effective removal of water from the moist corn plant and the supplement.

The weight of whole maize plants during the test period of 120 minutes was 9,108 kg (20,080 pounds) and the amount of feed supplement concentrate was 953 kg (2,100 pounds). the Amount of ruminant feed containing pelletized supplements / caught in the product hopper 3,810kg (8,400 pounds).

The recovery of protein equivalent during the entire process, rens was 93.4%. The corn pellets produced in this way were hard and neither dusted nor broken during normal operation Handling. The surface was surprisingly capable of soybean oil addition with aureomycin and other drugs which were applied in an amount of 1% without the lining becoming sticky or difficult to handle. These 1% application of soybean oil was done

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by spraying directly onto the pellets as they have been discharged from the pellet cooler by the belt conveyor.

Example 4

This example shows that it is not necessary in practice pure urea as the amide nitrogen source in the invention to use. For this experiment, an amide mixture was used by partial pyrolysis of urea to form a biuret produced by known processes, whereupon water and attapulgus clay were added to the pyrolysate. The composition the mixture obtained, here simply called "amide liquid" was designated as follows:

Component %

Biuret 19.1

Urea 43 , A.

Tone 2.0

Water 34.5

Triuret 0.2

Cyanuric acid 0.8

Total nitrogen 27.85

Protein equivalent 174

The alfalfa grass used in this example was used during the Harvested in autumn in central Nebraska. The composition was as follows:

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5 , 65 71 »Β O , 9 2 / 7 19th , 0

Component %

protein

Moisture fat

ash

Polysaccharides

These polysaccharides are of 2 general types: those that make up the skeletal structure of the plant and those / represent the reserves of simple chucks. Both types of polysaccharide are high molecular weight polymers made up of individual pentose and hexose units. the Polysaccharides present in this particular feed are primarily insoluble. The reserve sugar polysaccharides accounted for 2.5% of the feed.

Processing was carried out in a manner similar to that in Example X. When the AIfalfagras arrived at the conversion plant, it was it dumped into the feed system, where the plants were shredded into small pieces so that sufficiently large ones Surface becomes available for a rapid reaction with the amides * The alfalf feed was then continuously added to the mixer transferred, where the amide liquid, superphosphoric acid and alfalfa were processed into a homogeneous mixture, which was acidic (pH about 2), the plant was operated for 8 hours at the following feed rates! Alfalfa 907 kg / h (2,000 pounds / h), Amide liquid 20.2 kg / h (44.6 pounds / h) and superphosphoric acid 2.0 kg / h (4.5 pounds / h). The analysis of the superphosphorus

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73 rO 15th 71 , 7 81 0.13 20th Ir 75 ο, ο, 2,

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Acid catalyst was the following:

Component %

P ₂ O ₅

% GeSaJtIt-P ₃ O ₅ as polyphosphate

Fe ₃ O ₃ Al ₃ O ₃ MgO SO ₄

The mixed components were fed into the continuously working rotary dryer with gas fumigation, which works practically under air pressure and also serves as a reactor. The dryer was operated in such a way that the reaction constituents could enter at one end and exit at the other end with as little back-mixing as possible, so that careful control was maintained with regard to the amount of water removed. Sufficient moisture was maintained throughout the dryer to allow polysaccharide to degrade by hydrolysis without charring the product. The outlet temperature of the solids was maintained at 88 ⁰ C (J! 90 ° F), and the moisture content of the unreacted material was maintained at 8.1%. The remaining moisture that had entered with the feed material was continuously removed from the combustion gases. Samples withdrawn from the solids flow of the dryer reduced Fehling's solution * The reducing character of the intermediate product shows the

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Presence of cellobiose and maltose structures.

The partially converted and free-flowing alpha feed was continuously removed from the rotary dryer. This intermediate had a dry appearance and low density with a large surface area. To this material continuously remaining sugar cane molasses at 6O ⁰ C (140 F) in a ratio of 3.18 kg / h (7 lb / hr) was sprayed. The melas were concentrated and contained approximately 65% polysaccharides, half of which were water soluble disaccharides. The molasses slightly reduced Fehlingfeche's solution, indicating the presence of carbonyl groups that had undergone aldehydic condensations.

The mixture with the partially converted amides and polysaccharides was placed on the pelletizer, where small particles of the mixture almost instantly increased to 352 kg /

2
cm (5,000 psig) was compressed and the temperature rose

to 102 ° C. The product was immediately withdrawn from the press zone of the machine to an isolated area under the Air pressure worked. In this district, the conversion between the partially degraded saccharides and amides was left adiabatic continue, keeping the temperature at 121 ° C (25O ° F) during a residence time of 15 minutes increased. The agglomerated particles about 9.5 mm (3/8 inch) in diameter and about 12.7 mm in length (102 inches) were then cooled. The cooled aggregate had a hard, homogeneous surface and good particle strength

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The amount of agglomerated product recovered was 285.4 kg / h (629.2 lbs / hr), and the product had the following composition:

Component %

Protein equivalent 24.4

(Nitrogen) 3.9

Phosphorus (as P ₂ ^) 0 * 5

Humidity . 5.8

U & r total introduced amount of nitrogen was added 11.2 kg / h obtained (24.6 lb / h) as a useful product, since the total protein was 97.6 * equivalent. No ammonia smoke was developed during operation. The small losses that occurred appear to be due to the treatment and dust.

Example 5

This example shows the performance of the product according to the invention as a protein substitute in ruminant feed. A part of the product prepared according to Example 4 was used for evaluation against the same nitrogen sources in untreated Taken from the shape. The tests were carried out in the laboratory using standardized in-vitro methods, namely, 4 samples were used for each material. A Jersey bull was introduced into the rumen with a Tubes of rumen fluid freshly drawn off and with water and phosphate buffer diluted. All samples were prepared in such a way that

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that each has the same nitrogen content, namely 1,800 micrograms in per ml of sample.

After the nitrogen products were added to the samples at the beginning and then every hour for 3 hours. The ammonia nitrogen was obtained from each sample separated by diffusion and then analyzed. The results of the tests can be found in the following table.

Table I.

Total ammonia nitrogen (NH ₃ -N) in micrograms / mi after the specified time in hours

Feed supplement 0 hours 1 hour 2 hours 3 hours

NH ₃ -H NH ₃ -H NH ₃ -Ή NH ₃ -H

used in Example 4

Urea biuret clay liquid

6.16 293.9 587.6 991.4

generated in Example 4

Feed pellets 45.7 147.9 147.9 149.7

From these results, it can be seen that in spite of adding them The amount of nitrogen for each sample of rumen fluid is the product prepared according to the method of Example 4 resulted in a more constant supply of ammonia nitrogen that could be effectively used by the animal while without treatment added urea allowed a rapid release of ammonia in the rumen fluid down to a level, that could cause serious hip poisoning problems.

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Example 6

The following example demonstrates the effectiveness of the product of the invention as a slow release nitrogen source in water.

Exactly 15 g of uncrushed and unbroken pellets of the product of Example 4 were placed in a 250 ml beaker. Then 150 ml of distilled water was added, the contents were gently whisked and then allowed to stand undisturbed for the duration of the soaking test. After the impregnation had taken place, the contents were again whisked through in order to obtain a homogeneous liquid phase, and 100 ml of liquid were removed with a pipette, with as little suspended solid as possible being sucked into the pipette. The contents of the pipette were filtered through a glass frit vacuum filter of medium. Porosity filtered to remove any entrained solids. The filter was washed several times with 10-15 ml portions of cold water and all of the filtrates were rinsed and transferred to a Kjeldahl flask. The nitrogen content of the flask was determined using a standardized method. The percentage of nitrogen released from the sample with impregnation was then calculated based on the original sample weight. A total of 20 samples of the product of Example 4 were used to obtain nitrogen release values at various times according to the following table.

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Table Il

Sample description Product from sample no.4

% Total nitrogen released from sample with impregnation

15 minutes

16

30 min 1 hour

28

Example 7

This example shows the use of the product according to the invention as a vegetable feed.

A lawn of hardy ryegrass in deep trays was created by applying the product of Example 4 to the soil surface at a rate of 90 kg (200 pounds) of nitrogen

about 4,000 m (1 acre)! For comparison purposes also uncoated urea pellets and ammonium sulfate crystals with the same nitrogen rate on grass in similar Shells applied. Each bowl of grass was leached twice, one week after fertilization and 6 weeks after fertilization, to mimic 38 ram (1.5 in) of rainfall. The dripping from each bowl "Fezte amount of water was 750 ml. In each trough the grass was cut periodically and the chips were then dried and weighed. The yields on dry grass from the various fertilizers with the times are summarized in the following table.

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BATH ORIGINAL

Table III Yield of dry grass from fertilized trays in g

Cutting time in Ta- product example- uncoated- ammonium gene after fertilization game 4 ter urea sulfate

14 21 27 35 45 60 72 90 110

This experiment shows that the product of Example 4 '! Over a extended period of time provides plant food and releases nitrogen much more slowly than urea or ammonium sulfate. The safe use of the product according to Example 4 was proven by the fact that even when applied no burning was observed at a fairly high rate of application, as indicated by the yellowing of the grass leaves. at Urea and ammonium sulfate showed some combustion.

2.0 1.9 1/3 6.3 5.3 4.4 5'7, 6.0 6.7 5.8 6.3 6.2 5.8 6.8 7/0 4.7 5.5 6.8 6.5 5, 0 6.0 5.2 2.4 2.2 5.2 2.7 2.5 5.5 2.4 1/0

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Example 8

The pelletized product of the invention is essentially an aggregated material. Compared to Example 6, this example shows the influence of agglomeration the nitrogen release of the pellets.

Take a sample of the pelletized agglomerated product Example 4 was made in a blender to a very smart particle size divided. The powder obtained was then put on cold-water-soluble and insoluble nitrogen by conventional methods analyzed. The results are summarized in the following table.

Table IV

Product total stick cold water cold water

substance content * insoluble soluble

in% N in% of N in% of

Total N Total N

shredded product
of Ex. 4 3.90 61.8 38.2

This example shows that 38.2% of the total nitrogen in the finely ground product of Example 4 is immediately more water-soluble Nitrogen is available to both animals and plants and that 61.8% of the nitrogen is slowly released If you compare these results with those of the Example? "; 6 the improvement in the release has been proven, which can be achieved by agglomeration, because example 6 shows

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that only 16% of the total nitrogen is present as water-soluble nitrogen after 15 minutes of soaking in water from the pellets are.

Example 9

This example illustrates the conversion of whole corn plants and complete feed supplement liquid to slow released nitrogen for animal feed when using ammoniated superphosphoric acid (solution A) as a reaction catalyst. A block of whole corn plants was harvested in central Nebraska in the fall. The entire plant consisted of about 50% yellow stalks, 25% stems, 12% leaves, 10% cobs and 5% pods.

The painting plants were in the field 2 days after cutting to the conversion plant used in Example 1. The analysis of the grain plant was as follows:

Component %

Protein 2.5

(Sticker fabric) o, 4

Humidity 67.0

Fat I 0.8

Sugars (polysaccharides) 1.6

Carbohydrates (polysaccharides) 22.3

Ash 1.5

After the chopping, make-up liquid became continuous. added in a feed-amide mixer, namely the amount

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including addition of about 50 kg (HO pounds) per ton of corn plant feed. The composition of the feed supplement liquid in GeT The weight of the components per ton was as follows:

component

complement
kg / t pounds / t 322.0 146.1 20.0 700.0 317.5 463.6 210.3 140.0
0.44 63.5
0.20 1.44 0.65 0.08 0.04 1.44 0.65

Solution Λ ammonium sulphate cane molasses urea

Sodium chloride Copper sulfate Manganese sulfate Cobalt sulfate Zinc sulfate

After blending, the mixture was made from corn plants and supplement Heated at 94 ° C (200 ° F) at air pressure for 5 minutes in the continuous rotary dryer to remove the polysaccharides activated by partial decomposition, partial drying and reaction with the urea.

Upon discharge from the rotary drier, a sample exhibited a moisture content of 8.8%, and the test with Fehling * shear solution showed the presence \ C "~ \ reducing carbonyl groups. The product has a dry appearance and feel when GIFF only slightly tacky This material was continuously brought to the high temperature and pressure pelletizer machine that served as the agglomerator The mixture was suddenly brought to 422 kg / cm ² (6,000 psig) and heated to 108 ° C (226 ° F) and then isolated Area where implementation adiabatically progresses for 15 minutes

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BATHROOM 0RK3INAL

could. The temperature rose to 113 ° C (235 ° P) before the product became hard shiny particles of about 16 mm (5/8 of an inch) Diameter) and approximately 13 mm (3/4 inch) in length. The product obtained had the following composition:

Component %

Protein equivalent '14.8

Phosphorus (as ^p o ^ 5 ^ ^lf ^

The total amount of nitrogen fed into the process was

9.8 kg (21.6 pounds) hourly per ton of corn plant feed during an 8 hour operation, and the amount of nitrogen recovered in the finished hard pelletized product was

8.9 kg (19.7 pounds) hourly per ton of corn plant fodder, which means a protein equivalent gains performance of 91.2%. The entire amount of the extracted in the 8-hour operation Product was 378.3 kg (834 pounds) hourly per ton Corn plant feed.

Example 10

The following example shows that the product of the invention is non-toxic to ruminants. The toxicity level of urea in sheep is by various experts been communicated. It emerges as fairly certain from the literature that urea intake levels of about 15 g each 45.4 kg (100 pounds) animal weight on a single feeding result in toxic toxicity of concern and usually death of the animal

^leads * 209885/1380

Four sheep in the range of 45 to 50 kg (100-110 pounds) were taken out of feed and in a pen for 24 hours left starving. After these 24 hours, the sheep were forcibly fed with 1 kg of the product from Example 9 each. The amount of nitrogen fed to the sheep was equivalent to about 50 g urea per animal.

The ties were observed for 3 days and showed no signs from urea poisoning * You were slaughtered after 10 days, and no abnormalities were found when the bodies were examined.

Example 11

The agglomerated product produced according to Example 9 was tested in the laboratory for ammonia release rate compared to the Feed supplement liquid tested, which was used in example 9 for the supply of synthetic nitrogen. The evaluations were carried out using the tests described in Example 5.

The results of these tests can be summarized as follows * The ammonia nitrogen release rate was in the agglomerated Product significantly slowed down, and the nitrogen concentration after reaching a level of 265 mg N / ml rumen fluid showed a safe consumption level. the The release rate for this material was slightly higher than in the example 4, because the nitrogen source, a feed supplement

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concentrate of the liquid, some ammonium residue. The liquid feed concentrate of siqh resulted in a rapid and possibly dangerous release of ammonia in the rumen fluid, since the ammonia nitrogen level is around 1,000 micrograms / ml reached in 3 hours.

Example 12

The feeding experiments according to this example were carried out in order to increase the efficiency of the present method for the implementation and agglomeration of artificial amides, such as urea and biuret, slowing down their release in ruminants and thereby to prove the protection of ruminants from accidental overdosing of artificial nitrogen. In the Methods used in this example are not recommended as an appropriate feed diet for ruminants *

The toxic dose of urea in a single feeding is too about 70 g for horned cattle; Considerable values have been reported for animal feed in the veterinary literature indicating that an intake of 100 g or more of urea is serious Causes toxicity * which usually leads to animal death.

Three black Angus calves weighing approximately 270 kg (600 pounds) took 1.8 kg (4 pounds) daily using the method of the example 4 produced product, but the 37% protein equivalent compared to the 24.4% protein equivalent of the example 4 contained. This amount of feed meant the intake of the equi-

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valentes of 23Og urea daily. The animals showed none Signs of poisoning during the three day test period.

A fourth black Angus calf weighing 270 kg was born fed 2.7 kg (6 pounds) of the material prepared according to Example 4, but containing 33% protein equivalent. The pelletized product was broken into pieces and force-fed in a water slurry almost instantly. This amount of food particles contained the nitrogen equivalent of 313 g of urea, but did not show any signs of poisoning emerged. The next day, the same animal was further fed the same feed particles in an amount equal to the nitrogen containing equivalent of 220 g urea, and on the third day the same animal was given further identical feed particles fed in an amount that is the nitrogen equivalent of Contained 240 g urea. The animal showed no signs of urea or ammonia poisoning during the entire test period. 10 days after the last introduction of the PrüffUt-? Particles, the animal was slaughtered. Examination of the body showed no abnormalities.

A fifth black Angus calf was starved for 48 hours. Then it was forcibly fed through a pipe with about 2.3 kg (5 pounds) of broken but unground feed rolls, which were prepared similarly as in Example 9, but contained 28% protein equivalent. This one-time introduction of feed particulate nitrogen was equivalent to 220 g of urea. The animal showed no sign of intoxication.

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A sixth black Angus calf from the same pen as the other five, which also weighed approximately 290 kg, were used to prove the fact that the animals were urea poisoning documents. The animal was forcible with 140 grams of urea crystals in several gallons of water at 11:30 a.m. fed. At 'noon the animal showed signs of poisoning and died of severe poisoning at 2:00 p.m.

Example 13 .

This example illustrates the preparation of a non-pelletized one Slow-releasing nitrogen product made from AIfalfa hay, collected from several Nebraska fields in summer and early Autumn was harvested and dried in the sun> before it was transported to the feed production facility. The composition of a typical sample of Alfalfa hay was as follows:

Component %

Protein > 10.1 to 12.1

Humidity 27.1 to 29.8

Fat (ether extract) 1.7 to 2.4

Crude fiber (polysaccharides) 18.1 to 19.9

Ash 6.3 to 7.3

Prior to its use, the hay was passed through a chopper, in which it was chopped into particles of workable size became.

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In order to provide the acidic catalyst for the conversion as well as urea and other nutrients, a feed supplement liquid was created used, which was prepared by mixing the following ingredients:

Component . % in the mix

Solution a 30.0. Ammonium sulfate crystals 10.0 aqueous urea solution (65%
Urea) 40.0 CaCO ₃ (powdered limestone) 5.0 Water (total moisture 42.0%) 15.0

100.0

Since the supplement contained some suspended solids, the liquid was stirred during storage before use, to prevent the solid matter from settling. The feed supplement liquid contained 106% protein equivalent and had the following composition:

Component %

Nitrogen 17.1

Protein equivalent 10.60 phosphorus 4.6

Sulfur 2.5

Calcium 2.0

The chopped up alfalfa hay and the feed supplement liquid: were continuously fed into a conventional mixer at a rate of about 3 tons per hour of alfalfa hay and about 318 kg

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(700 pounds) of feed supplement fluid introduced hourly with rates during the 2 hour test period possible were kept constant. The rate of supplementary feed varied by one protein equivalent as required maintain from about 23 to 24% in the dry finished product.

The moist soaked hay formed in the blender became fed to a conventional gas fired continuous rotary dryer which also served as a reactor. The dem Dryer-fed combustion sgas.e were kept at about 132O ° C (2,400 ° F) to make water from the soaked hay effective to remove. The dryer was appropriately controlled to produce a dry product at a temperature of about 82 ° C (180 ° F) to deliver. The dry product contained about 8% Water. The residence time in the dryer was about 10 minutes. The dried product, which slowly released nitrogen, was cooled to ambient temperature of about 24 ° C (7: 5 ° F) and stored for use as described in Example 14. It contained about 23.5% protein equivalent and about 51% total digestible nutrients. For the sake of simplicity, the product of Example 13 hereinafter referred to as Product A.

Example 14

Feeding smokes were carried out to improve performance of the method of the invention by supplying ruminants with nutrient-balanced amounts of product A of Example 13 and ener.gJ.erejLche Jfiederkäuerfutterstof fe

2234813

Fat, starch, corn, etc. were fed. The feeding attempts were performed by feeding sheep weighing from 27 to 32 kg (60 to 70 pounds). The efficiency of the feed resulted from the weight gain of the sheep over the course of a test period of 30 days.

A group of 10 sheep were fed a mixed ration containing approximately 63% total digestible nutrients and approximately 6.6% protein equivalent. The palatability of the feed to show and to reach as large weight gains of the ruminant, the food was unlimited or offered for free choice. The weight gain values were taken over a test period of 30 days followed by a seven-day period to allow adaptation to the feed. The composition of the ruminant feed ration used in the feeding test is given in the table below.

Composition of the feed ration used in the test sheep

component

Product A corn barley molasses starch fat straw

ration
kg per ton
lb 150 330 121 266 165 364 45 100 45 100 18th 40 363 800

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This ration is nutritionally balanced according to known feeding standards.

The ration was ground to a flour by grinding and then in an extruder type pelletizer pelletized. However, the ration may be desirable can also be fed as flour.

The mean daily weight gain with the test ration sheep fed was 108 g (0.24 pounds) per day and Sheep during the 30 day trial. The adaptation of the animal to the feed was within the 7 day adaptation period excellent. The average nitrogen retention of ruminants was around 25%, which is a good one Equilibrium nitrogen weight.

In a comparative experiment, sheep were made in the same way fed the same ration as above, but were given 144 kg (318 pounds) of dehydrated alfalfa and 0.4 kg (12 pounds) Urea used instead of the 150 kg (330 pounds). Product A. This ration with urea supplementation was adjusted to the feed was relatively poor and the average daily weight gain of the sheep was only 32 g (0.07 pounds) daily per sheep during the 30-day test. So it can be seen that the weight gain of those with urea supplementation fed animals was considerably lower than that of the animals fed with the nitrogen slowly releasing product were fed according to the invention.

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Example 15

This example shows that waste or by-product carbohydrate material can be used in the method of the invention.

The by-product carbohydrate material used in this example

n /
was pulp from oragen after juicing and drying. the

The composition of the orange pulp was:

Component %

Polysaccharides 48.1

Humidity 10.1

Ash 5.1

Nitrogen 0.4

These polysaccharides are of two types; those who the Form the skeletal structure of the orange, d. H. Fiber »insoluble in water and water-soluble polysaccharides including simple sugars. The polysaccharides present are primarily of an insoluble nature.

400 parts of the dried orange pulp were mixed with 10 parts of solution A and 100 parts of aqueous urea containing 40 parts of urea. The resulting mixture was reacted in a rotary dryer for 25 minutes and dried at air pressure, the temperature of the reacting mass being maintained at about 96 ° C (205 ° F) by external heating of the reactor. Samples of the reaction mixture were tested with Fehling's ¹ shear solution and showed the presence of aldehydic

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Carbonyl groups.

The partially reacted material was then was heated, so that no active bacteria or worms there were mixed with 50 parts of municipal sewage sludge, the 20 minutes 104 ⁰ C (22O ° F). The composition of the sewage sludge was as follows:

Component %

Polysaccharides 51.0

Ash 18.1

Nitrogen 4.1.

Phosphate (as P ₃ O ₅ ) ² ' ⁵

Humidity 2.8

The sludge reduced Fehling's solution, indicating the presence of aldehydic carbonyl groups.

The resulting mixture was then formed into pellets approximately 9.5 mm long and 9.5 mm in diameter (3/8 inch), and the Pellets were in an autoclave for 1 hour at 116 ° C (24O ° F)

heated. The pressure in the autoclave was determined by means of pressurized nitrogen

2
maintained at 70 kg / cm (1,000 psig). After 1 hour the pressure was released and the pellets allowed to cool to ambient temperature. The composition of the product obtained was as follows:.

Component %

Protein equivalent 30.1

Humidity 5.1

20 98 85/1 3 80

Phosphate (as P ₂ ° 5)

The total accumulation of hard, slow release nitrogen particles was 97%. Similar results were obtained when adding bagasse, peanut hulls, wheat straw, and waste paper to the
Place of the dried orange pulp were used.

Example 16

This example demonstrates the use of a urea-formaldehyde solution, hereinafter referred to as solution B, in
carrying out the method of the invention. Solution B becomes
manufactured according to U.S. Patent 2,652,377. It contains about 15% water and about 85% dissolved urea-formaldehyde solids. The latter are bound in a molar ratio of formaldehyde to urea of about 4.6: 1.

The by-product carbohydrate material used in this example was juiced and oranges pulp
Drying. The composition of the orange pulp was the same as in Example 15.

The partially reacted material obtained was then sprayed with 50 parts of Solution B so that the solid material was coated. The mixture then became pellets of about 9.5 mm
Length and 9.5 mm diameter deformed, and the pellets were heated in an autoclave to 116 ° C (240 ⁰ F) for 1 hour.
The pressure in the autoclave was increased to about

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70 kg / cm (1,000 pslg) held. After 1 hour the The pressure was released and the pellets were allowed to cool to ambient temperature.

The total accumulation of hard particles with slow release of nitrogen was 97%. Similar results were obtained when using bagasse, peanut oil, wheat straw and waste paper instead the dried orange pulp were used.

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Claims (2)

Claims 'l. \ Process for the preparation of a protein substitute in ruminant feed as well as a material suitable as a fertilizer for plant growth with a slow release of nitrogen, characterized in that one a) a solid carbohydrate material containing water-insoluble polysaccharides with an aqueous solution of a Amides, such as ureaSBiuret, formamide or acetamide and an acidic catalyst that is non-toxic to ruminants is, soaks and the polysaccharides to be reactive with the amide Hydrolyzed carbonyl groups, b) the impregnated solid material at a temperature in the range from 70 to 145 ° C (160 to 290 ⁰ F), based on the temperature of the solid material, dries and converts to a slowly releasing nitrogen product, the amide-polysaccharide adducts and at least contains about 5% water, and c) the product is cooled to ambient temperature. 2. The method according to claim 1, characterized in that the amide consists of urea and the slowly nitrogen-releasing product is ^{pelletized at a temperature of about 60 to 150 C (140 to 300 0} F) before cooling. 3. The method according to claim 1, characterized in that the 20 988b / 1380 acidic catalyst made from superphosphoric acid or air anonized Superphosphoric acid and the amide consist of urea. 4. The method according to claim 1 and 2 ,, characterized in that that the intermediate containing the amide-polysaccharide adducts with a concentrated aqueous urea-formaldehyde solution at 60 to 90% total solids and about 0.5 up to 6.5 mol% of formaldehyde per mole of urea is coated. 5. The method according to any one of claims 1 to 4, characterized in that that a supplement liquid is used to impregnate the solid feed, which is an aqueous one Urea solution, a water-soluble sulfate, and superphosphoric acid optionally contains in ammoniated form as a catalyst. 6. The method according to claim 5, characterized in that the feed supplement liquid is set so that they have a nitrogen to sulfur ratio of not more than 15 parts by weight of nitrogen in the total feed 1 part sulfur and a weight ratio of nitrogen to phosphorus of not more than 8 parts nitrogen per 1 Part of phosphorus yields. 7. The method according to claim 6, characterized in that up to 2% of the total weight of a water-soluble poly saccharide is introduced into the feed stock before pelletization, 8. The method according to claim 5, characterized in that one part by weight of feed supplement liquid with 6 to 10 parts by weight of solid ruminant feed is mixed. 9. The method according to claim 5, characterized by the use of alfalfa grass or maize plants as solid ruminant feed . 10. The method according to any one of claims 1 to 5, characterized in that that drying and reaction are based on a temperature in the range of 82 to 115 ° C (180 to 240 ° F) the temperature of the solid feed can be carried out, the residence time at the drying temperature 5 to 60 minutes. 11. The method according to claim 5, characterized in that the solid ruminant feed has a water content of 25 to 75% by weight and the water content of the dried impregnated solid feed is 6 to 12% by weight. 12. The method of claim 5 characterized in that the pelletizing temperature is 60 to 150 ° C (140 to 300 ° F). 209ööb / 1380 13. The method according to claim 5 _f, characterized in that the pelletized product is cooled to ambient temperature within 1 to 60 minutes after pelletization. 14. The method according to claim 5, characterized in that the solid ruminant feed with a urea pyrolysis product supplement containing urea and biuret. 15. Means for feeding ruminants, containing carbohydrates and protein, characterized by a supplemental nitrogen source consisting of a water-insoluble urea-polysaccharide adduct in sufficient quantity to achieve a total nitrogen content of about 2 to 10% by weight with a water-insoluble nitrogen content of 50 to 90% of the total nitrogen. 2 098 86/1380