High integrity natural nitrogenous granules for agriculture

A method of preparing high integrity natural nitrogenous granules for agriculture by heating natural nitrogenous materials under alkaline conditions until the materials develop adhesive properties, forming the materials into granules by mechanical means, and heating the natural nitrogenous granules until they harden; and the compositions formed by this method. The granules for agriculture include natural fertilizers, secondary nutrients, micronutrients, and natural animal feed protein supplements. The method also provides natural based plant food and animal feed supplement granules containing natural or synthetic additive substances which are useful in agriculture. The natural materials used in the method include poultry waste, poultry feather meal, hair meal, seafood meal, blood meal, bone meal, soybean meal, food waste, and grain by-products. The method provides natural nitrogenous granules which are free of disagreeable odor by admixing reactive aldehyde compounds with the natural nitrogenous materials prior to granule formation.

FIELD OF THE INVENTION 
This invention is directed to the use of natural materials as plant foods 
and animal feed supplements and more particularly to the conversion of low 
value, or worthless, natural by-products and wastes to valuable granules 
which have high physical integrities and are valuable products for use in 
the field of agriculture. 
BACKGROUND OF THE INVENTION 
During the recorded history of man, nitrogenous natural materials have been 
used as plant foods and animal feeds. The nitrogen in natural materials is 
usually present as one or more of a wide variety of proteins. These 
proteinaceous materials, when used as plant foods or animal feeds, 
decompose slowly into mineral nitrogen compounds which can be readily 
utilized by growing plants without damage to the environment in which they 
are used. They can also be effectively digested and utilized by animals 
consuming them. 
As world population density has increased several important changes have 
occurred in the availability and use of the proteinaceous materials. 
Virgin nitrogenous natural materials are now usually too valuable for use 
as plant foods or animal feed supplements. Huge amounts of natural 
by-products and natural wastes are produced after the primary, and perhaps 
secondary, usages of the nitrogenous natural materials and present a large 
disposal problem. Most of this natural material is available in dilute, 
low bulk density, amorphous, mixed forms and are generally commercially 
unusable in agriculture. Some of these natural materials commonly 
available in excess are by-products and wastes from processing grains such 
as soybeans; and by-products from processing animals such as poultry, 
cattle, and swine. Other widely available nitrogenous natural materials 
are wastes from animals, and recovered sludges from sewage treatment 
plants. 
In U.S. Pat. No. 3,655,395 John Karnemaat disclosed a process for treating 
industrial and municipal wastes suspended or dissolved in water by 
stepwise treatment with concentrated formaldehyde, nitric acid, and urea 
to form urea-formaldehyde condensation products which were then dried. 
Industrial and municipal wastes generally contain sufficient heavy metals 
to be unacceptable for many agricultural and environmental uses, and must 
be disposed of in special ways. Karnemaat extended his technology in U.S. 
Pat. No. 3,939,280 which teaches converting poultry manure to animal feeds 
by treatment with a catalytic amount of a non-toxic acid, such as 
sulfuric, phosphoric, citric, propionic and acetic, and with a 
formaldehyde supplying substance and urea. Although Karnemaat provided a 
step forward in the art of waste disposal, he did not recognize that 
natural nitrogenous materials could be caused to develop adhesive 
properties by heating under alkaline conditions, and that the natural 
materials could be formed into high integrity granules by mechanical means 
without polymerized urea-formaldehyde. Further, by adding substantial 
amounts of extraneous materials Karnemaat converted the initial natural 
organic material to a urea formaldehyde condensation product. 
In U.S. Pat. No. 3,942,970 O'Donnell discloses a system for producing a 
granular, high nitrogen, odorless fertilizer from sewage filter sludge, 
which required addition of acid to bring the pH of the sludge to between 3 
and 5, and then reacting it with methylolurea at pH 3-5, at 30.degree. to 
80.degree. C. with vigorous agitation at temperatures of 30.degree. to 
80.degree. C. to provide a granular reaction product of condensed urea 
formaldehyde polymer combined with the dried sludge. In U.S. Pat. No. 
4,081,366 O'Donnell dewatered the urea formaldehyde-sludge mixture by 
means of vacuum filtration. The acid catalyzed reaction of O'Donnell 
denatures the natural proteins present in the sludge, thereby 
significantly reducing their effectiveness as animal feeds or fertilizers. 
No mechanical means was provided to produce high integrity granules from 
the natural materials. O'Donnell did not recognize that heating natural 
nitrogenous materials under alkaline conditions could provide the adhesive 
properties required to produce high integrity natural granules. 
In U.S. Pat. No. 2,977,214, J. H. McLellan was able to produce granules of 
natural nitrogenous sewage sludge by compacting between high pressure 
rolls, breaking the compacted sludge and screening it. Unfortunately the 
particles referred to as granules were not dense, having a bulk density of 
only 35 pounds per cubic foot indicating a low degree of integrity. 
The art has recently taken strong interest in the use of natural 
nitrogenous materials as plant food and animal feed supplements with a 
plethora of publications demonstrating their utility in agriculture. The 
products disclosed have largely been the result of composting, extrusion, 
compacting, pelletizing, or inclusion in resinous agglomerates. No 
teachings or suggestions have provided a method of forming these natural 
materials, wastes, and by-products into high integrity granules by heating 
under alkaline conditions until they develop adhesive properties. 
Terms used herein are defined in the following list: 
1. Natural nitrogenous materials--any substance occurring in nature formed 
by living organisms and containing nitrogen, including processing 
by-products and wastes, usually in the form of protein or complex organic 
nitrogen compounds such as uric acid. 
2. High integrity--high degree of soundness, strength, and resistance to 
attrition. 
3. Adhesive property--the capability of bonding surfaces together by 
surface attachment. 
4. Water soluble nitrogen--soluble in water as defined by the Association 
of American Plant Food Control Officials (AAPFCO). 
5. Harden--to make not soft but solid and firm to touch. 
6. Liquid phase--the liquid portion of a mixture containing liquid and 
solid under process conditions. 
7. Chopper--device for cutting into small pieces by hitting with sharp 
knives or bars. 
8. Substantial--large enough to affect physical properties. 
9. Percent--weight percent. 
10. Agriculture--the industry of producing crops and animals employing 
plant foods and animal feed supplements. 
11. Basic Conditions--where pH is between 7 and 14. 
12. Base--class of compounds producing pH's between 7 and 14 and having the 
ability to neutralize acids. 
13. Agricultural Nutrient Substances--synthetic or natural materials 
normally used in the field of agriculture as plant nutrients or animal 
feed supplements. 
OBJECTS OF THE INVENTION 
It is a primary object of the present invention to provide a method of 
preparing high integrity natural nitrogenous granules for agriculture from 
natural nitrogenous materials. 
It is a further primary object of the present invention to provide a 
composition of high integrity nitrogenous granules which is useful in 
agriculture. 
It is a further primary object of the present invention to provide a method 
of preparing high integrity natural based nitrogenous granules for 
agriculture from natural nitrogenous materials and added agricultural 
nutrient substances. 
It is a further primary object of the present invention to provide a 
composition of high integrity natural based nitrogenous granules for 
agriculture which contain added natural or synthetic agricultural nutrient 
substances which are useful as agricultural nutrients. 
SUMMARY OF THE INVENTION 
The present invention is directed to a method of preparing high integrity 
natural nitrogenous granules for agriculture from natural nitrogenous 
materials which may be nitrogenous products found in nature, but usually 
are natural by-products, or wastes, from the agricultural industry. 
The method involves heating the natural nitrogenous material under basic 
conditions until this material develops adhesive properties, forming the 
adhesive material into granules by mechanical means, and continuing to 
heat the granules until they harden. 
I have discovered that with proper heating of natural nitrogenous materials 
under basic conditions in the present of moisture, hydrolysis of the 
nitrogenous material surfaces occurs making the surfaces sticky so that 
the materials develop adhesive properties and may be formed by mechanical 
means into granules. When these granules are heated further granules 
harden and develop a high degree of physical integrity. 
I have also discovered that compositions prepared by the method of this 
invention are effective for use in agriculture, particularly as 
fertilizers, secondary nutrients, micronutrients, and animal feed protein 
supplements. 
It was found that additional other agricultural nutrient substances may be 
included with natural nitrogenous materials in the method of this 
invention so long as the total of these added substances do not exceed 
one-half of the weight of the final product, thereby diminishing granule 
integrity. 
It was also found that the method of this invention produced natural based 
nitrogenous granules for agriculture which exhibited no disagreeable odor 
when a small amount of aldehyde compound reactive with amines and 
mercaptans was mixed with the natural nitrogenous materials prior to the 
heating under basic conditions to develop adhesive properties for granule 
formation. 
It was also found that the integrity of the granules was improved when the 
granules formed under basic conditions were neutralized with acidic 
materials. 
DESCRIPTION OF PRESENTLY PREFERRED EMBODIMENTS 
The method of the present invention prepares natural granules which have 
exceptionally high integrity, that is they are hard, strong, and resist 
attrition when abraided by rough handling, shipping or applying. The 
granules are particularly effective in agriculture for use as natural 
plant nutrients and animal feed supplements because their high physical 
integrity has been created without changing the desirable compositions of 
the natural nitrogenous starting materials. 
A wide variety of natural nitrogenous materials are available in the 
environment and as wastes or by-products in the agricultural industry 
which may be effectively used in the present invention. I have found that 
when these materials are heated under basic conditions that the surfaces 
of the materials develop adhesive properties and that granules may be 
formed by mechanical means while the natural materials have adhesive 
properties. Surprisingly, if granules formed from the adhesive materials 
are heated further, the granules harden, lose their adhesive properties, 
and become free-flowing high integrity granules. 
The adhesive properties were found to develop as a result of base catalyzed 
surface hydrolysis of natural proteins and complex nitrogen compounds, and 
the presence of moisture in amounts between 5 and 70 percent by weight was 
found to be necessary to produce hardened granules of high integrity in a 
reasonable treatment time. Higher moistures made the mechanical means for 
forming the granules difficult to operate and slowed the hardening of the 
granules, while lower moistures slowed the development of adhesive 
properties. 
The development of the adhesive properties in the natural nitrogenous 
materials requires that some of the natural nitrogen be in the water 
soluble form. It was found that satisfactory operation could be obtained 
when the natural nitrogenous materials were heated until between 5 and 50 
percent of the natural nitrogen was water soluble. Lower amounts caused 
poor adhesive properties and higher amounts caused the mixture to form 
large balls or globules in the mechanical granulation, producing 
unsatisfactory operations and product. 
The heating required to develop adhesive properties in the natural 
nitrogenous materials under basic conditions may be varied somewhat 
depending upon the materials used, but adhesive properties were 
satisfactorily developed at temperatures between 50.degree. and 
100.degree. C. when held for periods of time between 3 and 60 minutes. 
Longer periods of heating produced too much hydrolysis and materials too 
wet for effective mechanical granulation. Temperatures higher than 
100.degree. C. or treatments with acid caused the denaturing of the 
proteins in the natural materials reducing their availability in animal 
feed supplements and slowing their release of nitrogen in plant foods. The 
heating may be done by conventional means such as direct injection of 
steam, or heating in a jacketed vessel. When the heating is done, it is 
necessary that the natural materials be moving, stirred, or agitated so 
that heat transfer to all particles is good with none of them being 
overheated. 
Rotary drum granulation, compacting, punch and die pelletizing, and 
extrusion were all found to be unsatisfactory means of forming granules 
from natural nitrogenous materials, producing low density, low strength, 
dusty, and low integrity granules. 
Mechanical means were found by which high integrity granules could be 
prepared from the adhesive natural nitrogenous materials. The preferred 
means was a stationary granulating cylinder containing mixing elements 
mounted onto a rotating central shaft traversing the cylinder which throw 
the natural materials toward the center of the granulating cylinder. These 
mixing elements run close to the wall of the cylinder and prevent the 
adhesive materials from sticking to the wall. The mixing elements are 
operated at a speed sufficient to force axial and radial flows 
simultaneously on all the particles of material in the cylinder creating a 
mechanically fluidized bed. The action of the fluid bed causes the 
adhesive materials to form nearly spherical granules in the open space of 
the granulating cylinder. The size, shape, peripheral speed of the mixing 
elements may be regulated to match the physical properties of the 
individual natural nitrogenous materials used to form closely-sized 
granules. 
It was found that the particle size range of the granules prepared in the 
stationary granulating cylinder could be narrowed by equipping the 
cylinder with one or more independently driven choppers mounted in the 
side wall of the cylinder to break lumps and control particle size. 
Depending upon the length of the granulating cylinder the number of 
choppers employed is varied, with the distance between choppers along the 
cylinder wall amounting to about two diameters of the granulating 
cylinder. 
Although the granulation was effectively carried out in the mechanically 
fluidized bed it was found that granulation could be improved still 
further when fluidization was assisted by the upward flow of air through 
the natural nitrogenous materials during granulation at linear velocities 
between 0.5 and 5.0 feet per second. Further, it was found that the air 
flow improved the hardening of the granules. 
After the granules were formed by mechanical means from the adhesive 
materials it was found effective to continue to heat the granules at a 
temperature between 75.degree. and 100.degree. C. for a period of time 
between 5 and 20 minutes until they harden, and no longer show adhesive 
properties. 
When the granules have been hardened, they still may contain more water 
than desirable from the standpoints of storage stability, and shipping 
economics. It was found that these desirable conditions may be obtained by 
an additional step of drying with warm air at temperatures between 
80.degree. and 110.degree. C. until the granules contain between 0 and 8 
percent water. 
Most of the natural nitrogenous materials have near-neutral pH's and it was 
found necessary to admix a base to the material to improve the development 
of its adhesive properties when it is heated. Alkali metal hydroxides such 
as sodium and potassium hydroxides are economical and particularly 
effective bases for assisting the formation of adhesive properties. It was 
found that the use of these alkalis in amounts between 1 and 10 percent of 
the materials are particularly effective. It is necessary to the safe, 
effective use of the granular products, that the strong basic pH's created 
by these strong bases be neutralized after granules are formed and the 
neutralization improves the physical integrity of the hardened granules. 
The natural nitrogenous granules prepared by the method of this invention 
are effective as plant foods and these granular plant foods may be 
prepared from a single natural nitrogen material or a combination of 
several natural materials. Some of the natural nitrogenous materials found 
to be particularly effective in preparing granular plant foods are: 
poultry waste, poultry feather meal, swine hair meal, seafood meal -- 
including fish meal, crab meal and shrimp meal, blood meal, bone meal, and 
soybean meal. 
When natural nitrogenous granules are prepared as animal feed protein 
supplements by the method of this invention one or more of the following 
natural nitrogenous materials was found to be particularly effective: 
soybean meal, poultry feather meal, hair meal, seafood meal, meat and bone 
meal, blood meal, food waste and grain by-products. 
The granule composition prepared by the method of the present invention is 
effective as a new product for use in agriculture. The composition was 
found to preserve the natural nitrogen values of the original in a form 
which is readily deliverable for effective release for agricultural 
utilization for a wide variety of uses. The granule composition was found 
to be particularly effective as a nitrogen plant food, releasing its 
nitrogen content in a slow but complete manner without hazard to the 
environment, after effective delivery to its use site. Similarly when the 
composition of this invention was utilized as a natural animal feed 
protein supplement, it was found that the protein content of the natural 
materials was preserved without denaturing so that it could be effectively 
metabolized as a protein supplementation by animals being fed 
commercially. 
The method of this invention was found to be particularly effective in 
preparing high integrity natural nitrogenous granular fertilizers from 
natural nitrogenous materials when those materials consisted of one or 
more of the following by-products or wastes: poultry waste, poultry 
feather meal, hair meal, seafood meal, blood meal, bone meal, and soybean 
meal. In this effective method, these materials are charged in a 
stationary granulating cylinder containing mixing elements mounted on a 
central rotating shaft which throws these natural materials toward the 
center of the granulating cylinder, forcing axial and radial flows 
simultaneously on the materials creating a mechanically fluidized bed, the 
fluidization being assisted by an upward flow of air through the fluidized 
bed at a linear velocity between 0.8 and 2.0 feet per second. For optimum 
effectiveness the granulating cylinder should be equipped with one or more 
independently driven choppers in the side wall of the cylinder to control 
the size of the granules formed. Using the method of the present invention 
it is most effective to admix aqueous alkali metal hydroxides amounting to 
between 2 and 5 percent on a dry basis with the natural nitrogenous 
materials which preferably contain between 10 and 35 percent water, to 
heat the mixture to a temperature preferably between 70.degree. and 
90.degree. C. for a period of time between 10 and 30 minutes to hydrolyze 
the natural materials until preferably between 15 and 40 percent of the 
natural nitrogen materials are water soluble and the nitrogenous materials 
develop adhesive properties. 
It was found preferable in the instant invention to form the nitrogenous 
materials into fertilizer granules by means of the simultaneously applied 
axial and radial flows in the air assisted, mechanically fluidized bed 
while the nitrogenous materials contain between 15 and 50 percent water 
and exhibit adhesive properties. Water may be added, if necessary, to 
bring the water content to the optimum level for granule formation, and it 
may be decreased to that level by dewatering or drying, if necessary. 
When the granules have been formed by mechanical means it is preferred to 
neutralize them to a pH between 6.0 and 8.5 by admixing acidic materials 
which are non-toxic, economical, and useful in fertilizers. Acidic 
materials found effective in this method include: sulfuric acid, 
phosphoric acid, acetic acid, ammonium phosphate, and ammonium sulfate. 
Once the fertilizer granules are neutralized they are preferably hardened 
by continuing to heat them in the granulating cylinder at a temperature 
between 70.degree. and 95.degree. C. for a period of time between 5 and 30 
minutes until they become free flowing. 
Although the hardened fertilizers are useful as fertilizers, it is 
preferred to dry them further so they will not mold, or spoil and water 
will not needlessly be shipped. This drying is preferably done by 
discharging the hardened natural fertilizer granules from the stationary 
granulating cylinder into a dryer operating with air exit temperature, 
after passing through the drying granules, of between 80.degree. and 
90.degree. C. The fertilizer granules are preferably held in the dryer 
until they contain between 1 and 5 percent water. 
The preferred method of preparing high integrity granular natural animal 
feed protein supplements is in an apparatus like that used in the 
preferred fertilizer method. The preferred natural proteinaceous materials 
for use in preparing these protein feed supplements are one or more of the 
following: soybean meal, corn gluten, poultry feather meal, hair meal, 
meat and bone meal, blood meal, seafood meal, and grain by-product. 
To prepare the granular animal feed protein supplements, aqueous alkali 
metal hydroxides, preferably amounting to between 3 and 6 percent on a dry 
basis, are admixed with the natural proteinaceous materials which contain 
between 10 and 35 percent water and heating the mixture to a temperature 
between 70.degree. and 90.degree. C. for a period of time, preferably 
between 10 and 40 minutes to hydrolyze the natural proteins until between 
5 and 20 percent of the protein nitrogen is water soluble and the 
proteinaceous materials develop adhesive properties. 
It is preferred to form the proteinaceous materials into animal feed 
protein supplement granules by means of the simultaneously applied axial 
and radial flows in an air assisted, mechanically fluidized bed while the 
proteinaceous materials contain between 10 and 35 percent water and 
exhibit adhesive properties. 
To obtain optimum safety, performance and physical integrity of the animal 
feed protein supplements it is preferred to neutralize the granules to a 
pH between 6.0 and 8.5 by adding acidic materials which are non-toxic, 
economical, and widely available. Some of these acidic materials found to 
be effective are listed as follows: phosphoric acid, sulfuric acid, acetic 
acid, fatty acids, ammonium sulfate, and ammonium phosphate. 
To harden the granular animal feed protein supplements it is preferred to 
continue to heat them in the granulating cylinder at a temperature between 
70.degree. and 85.degree. C. for a period of time between 8 and 15 minutes 
until they harden and are free flowing. 
Although the hardened granules are themselves useful as feed supplements, 
it is preferred to dry them by discharging the hardened natural feed 
supplement granules into a dryer, preferably a fluid bed dryer, operating 
with an air exit temperature between 75.degree. and 90.degree. C., and 
holding the granules in the dryer until their moisture content has been 
reduced to a level, preferably, between 1 and 10 percent water. 
Where completely natural products are not required, the method of this 
invention may be used to prepare natural based products containing other 
substances useful in agriculture, particularly synthetic and other natural 
agricultural nutrient substances. It was found that sufficient adhesive 
power is developed by the heated natural nitrogenous materials when they 
are heated under basic conditions to allow the formation of strong 
granules with up to 50 percent other substances added when the mixture is 
heated under basic condition and granulated by mechanical means. 
When applying the method of the present invention to preparing high 
integrity natural based nitrogenous granules for agriculture it was 
preferable to admix the other agricultural nutrient substances in amounts 
between 1 and 50 percent with the natural nitrogenous materials containing 
a substantial amount of water and then to heat the mixture under basic 
conditions until the nitrogenous materials develop adhesive properties. 
The adhesive materials may then be formed by mechanical means and heated 
further until they harden and exhibit free flowing properties. 
High integrity natural based nitrogenous granules for agriculture may be 
produced by the method of this invention as effective fertilizers where 
the nutrient substances amount to a total of between 10 and 50 percent of 
the weight of the free flowing granules. The nutrient substances 
effectively admixed with the natural nitrogenous materials include the 
synthetic or natural nitrogen, phosphorous, and potassium plant nutrients 
required to supply the complete nutrient requirement for plant growth. 
Synthetic nitrogen sources found to be effective as nutrient substances in 
the present invention include urea, ammonium sulfate, methylol urea, 
methylene urea, isobutylene diurea, crotonylidene diurea, ammonia, and 
ammonium nitrate. Care must be observed in handling, formulating, and 
heating potentially explosive ammonium nitrate. The slow releasing 
methylol urea, methylene urea, isobutylene diurea and crotonylidene diurea 
may be formed in-situ by the reaction of the appropriate aldehyde with 
urea. 
Phosphorous plant nutrient substances found to be effective in the method 
of the instant invention include phosphate rock, phosphoric acid, bone 
meal, ammonium phosphate, potassium phosphate and ammonium polyphosphate. 
The phosphate rock and bone meal are preferably ground to a fine powder 
prior to their use. 
Effective potassium plant nutrient substances in the present method of 
producing high integrity natural based fertilizer granules were found to 
include potassium chloride, potassium nitrate, potassium sulfate, 
magnesium potassium sulfate, potassium carbonate, and potassium phosphate. 
The natural nitrogenous materials available as wastes and by-products from 
agriculture usually contain valuable amounts of the secondary nutrient 
elements calcium, and magnesium. It was found that natural based 
nitrogenous granules can be prepared for agriculture which contain 
additional secondary nutrients and are useful as secondary nutrients for 
feeding plants. In this method, the substances found suitable for admixing 
with the natural nitrogenous materials were alkaline earth compounds and 
were, preferably, one or more of the following compounds: magnesium oxide, 
magnesium carbonate, magnesium sulfate, magnesium phosphate, calcium 
oxide, calcium carbonate, calcium sulfate and calcium phosphate. The 
integrity and storage stability of the granules are optimum when the total 
alkaline earth compounds added amounts to, preferably, between 2 and 20 
percent of the final product weight. 
The natural nitrogenous materials available usually contain enough 
micronutrients to enhance the value of the material as either a fertilizer 
or an animal feed protein supplement. By use of the instant method, 
natural based nitrogenous granules for agriculture may be produced which 
are suitable for use as micronutrient concentrates for plants or animals. 
To make these concentrates it was found that micronutrient substances 
could be added to the natural nitrogenous materials in total amounts 
between 0.5 and 35 percent and excellent granule integrity could be 
retained. Preferred micronutrient substances for addition consist of zinc 
oxide, zinc sulfate, zinc citrate, zinc chelate, iron sulfate, iron 
chelate, manganese sulfate and copper sulfate. 
The method of the instant invention may be used to prepare natural based 
nitrogenous granules for agriculture which are animal feed protein 
supplements, where it is desired to fortify the natural material with 
additional non-protein nitrogen sources, such as urea or biuret. It also 
may be desirable to fortify the phosphorous, potassium, calcium, 
magnesium, iodine, and other mineral levels of a natural protein 
supplement. It is also possible to further fortify the final dry granule 
by spraying or coating with single or multiple vitamin mixtures of value 
in animal health. It was found that free flowing high integrity granules 
of animal feed protein supplements could be produced when the total amount 
of animal nutrients mixed with the natural nitrogenous materials was 
preferably between 3 and 25 percent. 
It was found that the composition of natural based nitrogenous fertilizer 
granules prepared by the present method were uniquely effective and safe 
plant foods. The composition including urea, methylol urea, methylene 
urea, and the hydrolyzed natural nitrogenous material was found to safely 
release nitrogen and effectively grow long season plants with only one 
initial fertilizer application, clearly demonstrating the uniqueness of 
the present composition. 
The composition of the natural based nitrogenous feed protein supplement 
granules is unique. Its resistance to attrition, dust-free property, and 
particularly its homogeniety provide a feed supplement product with 
heretofore only desired properties and feeding safety. The proteins in the 
composition are highly available for animal digestion and use. 
Some of the available natural nitrogenous materials such as soybean and 
grain meals have pleasant odors and some of the natural nitrogenous 
materials which are by-products and wastes from the agricultural industry 
such as feather meal have only mild odors. Granules produced by the 
present method from mild nitrogenous sources may exhibit acceptable odors 
when treated with mild odorants such as cane molasses, eucalyptas oil, or 
mint extract. Some of nitrogenous materials, such as the wastes, have very 
disagreeable odors which continue to exist in the hardened granules formed 
from them. It was found that the problem of disagreeable odors in the 
granules could be eliminated by adding to the natural waste an aldehyde 
compound which is reactive with amines and mercaptans. Using this 
discovery in the method of the present invention a method was devised for 
granules with no disagreeable odors. 
In this method of producing natural based nitrogenous granules for 
agriculture which exhibit no disagreeable odor, between 1 and 10 percent 
of an aldehyde compound which is reactive with amines and mercaptans is 
mixed with natural nitrogenous materials containing a substantial amount 
of water. The mixture is heated under basic conditions to temperatures 
between 70.degree. and 90.degree. C. until no disagreeable odor persists 
and the nitrogenous materials develop adhesive properties. The mixture is 
formed into granules by mechanical means while the mixture still exhibits 
adhesive properties. The granules are heated further until they harden and 
exhibit free flowing properties. 
The preferred aldehyde compounds, reactive with amines and mercaptans were 
found to be: aqueous formaldehyde, aqueous methylol urea, aqueous urea 
formaldehyde concentrate, aqueous methylene urea, hexamethylene tetramine, 
acetaldehyde, crotonaldehyde, and propionaldehyde. 
The composition of the natural based nitrogenous granules for agriculture 
exhibiting no disagreeable odor prepared by the method of this invention 
using aldehyde compounds was unique in that it performed as satisfactorily 
as a nitrogen supplier, and stored and handled as well as the natural 
based granule compositions which were not treated to eliminate the 
disagreeable odors. 
The method of this invention was found to be applicable for preparing many 
products for agriculture from many sources of natural nitrogenous 
materials under the range of conditions defined herein. A preferred use of 
the present invention is a method of producing high integrity, low odor, 
natural based, granular fertilizers, in which aqueous formaldehyde 
amounting to between 1 and 5 percent, dry basis, between 0 and 30 percent 
urea prills, and between 0 and 30 percent soluble potassium chloride are 
mixed with natural nitrogenous composted chick waste containing between 40 
and 75 percent water. The mixture is heated at a pH between 8.0 and 11.5 
to a temperature between 70.degree. and 85.degree. C. and held for a 
period of time between 10 and 30 minutes until between 15 and 40 percent 
of the chick waste nitrogen is in water soluble form and the mixture 
develops adhesive properties. The mixture is formed into fertilizer 
granules by means of simultaneously applied axial and radial flows in an 
air assisted, mechanically fluidized bed, while the mixture still contains 
between 20 and 40 percent water and exhibits adhesive properties. The 
fertilizer granules are neutralized to a pH between 6.5 and 8.0 by adding 
mineral acid while the granules are still in the fluid bed. By continuing 
to heat the granules in the fluid bed at a temperature between 78.degree. 
and 85.degree. C. for a period of time between 8 and 20 minutes the 
fertilizer granules are hardened until they exhibit free flowing 
properties. 
The composition of high integrity, low odor, natural based granular 
fertilizers prepared by the method of this invention provide optimum 
product handling and storage properties and optimum performance properties 
for long term safe release of mineral nitrogen in soils for feeding plants 
.

The following examples illustrate the method of the present invention of 
preparing high integrity natural nitrogenous granules for agriculture and 
the efficacy of the composition prepared thereby. 
EXAMPLE 1 
Example 1 illustrates the method of preparing high integrity natural 
nitrogenous granules for agriculture by heating natural nitrogenous 
materials under basic conditions, forming granules by simple mechanical 
means and heating the granules until they harden. 
To an electrically heated laboratory stainless steel mixergranulator having 
a vertical cylindrical shape with an inside diameter of 20 centimeters, a 
height of 28 centimeters, and equipped with an agitator consisting of 4 
flat stainless steel bars, each 9.5 centimeters long, 2 centimeters high, 
and 0.5 centimeters thick, was added 500 grams of the natural nitrogenous 
material poultry feather meal. 
To the feather meal was added 150 grams of water, and 25 grams of sodium 
hydroxide. The agitator was operated at a speed of about 120 rpm and the 
mixture was heated to 80.degree. C. After about five minutes at 80.degree. 
C. the mixture became sticky, developing adhesive properties and granules 
formed. Agitation was continued and temperature was maintained between 
76.degree. and 85.degree. C. for an additional 15 minutes and the granules 
hardened. Heating and agitation were terminated and the contents were 
placed in an oven and dried with high velocity air circulation at 
90.degree. C. 
The granules were cooled and screened. The high physical integrity of the 
granules was indicated by their hardness. Although there was a wide size 
range of the near spherical granules produced there was no dust in the 
product and after shaking in a screening machine for 10 minutes no dust 
was created by attrition. Analytical determination of nitrogen in the 
granular fertilizer product showed a 12.8 percent nitrogen content, all of 
which was natural. 
EXAMPLE 2 
Example 2 illustrates the efficacy of the high integrity natural 
nitrogenous granule composition for agriculture prepared in Example 1 as 
plant foods. 
Common ryegrass was planted in twelve six inch diameter plastic pots 
containing soil depleted of nitrogen and after the seeds had germinated 
and the blade heights were about 1/2 inch high, four pots were treated 
with the product of Example 1 to provide nitrogen at a rate of 3 pounds 
per thousand square feet. Four pots were treated with urea to provide 
nitrogen at a rate of 3 pounds per thousand square feet, and the other 
four pots received no nitrogen. Each of the pots in the test received 
phosphorous pentoxide at the rate of 1 pound per 1000 square feet and 
potassium oxide at the rate of 0.5 pounds per 1000 square feet. Each pot 
was irrigated with water every third day at the rate of one inch per week. 
The pots receiving no nitrogen quickly showed stress and by the eighth week 
the few remaining blades of grass were brown. The pots receiving the urea 
nitrogen after one week showed strong burn stress with the blades mostly 
yellow. By the fourther week the urea treated grass stand was largely 
reduced by dead grass blades and most of the remaining blades were yellow. 
After the sixth week the urea treated grass contained a few remaining 
grass blades which were green and growing rapidly. After the eighth week 
the few urea treated grass blades remaining had about stopped growing and 
were showing signs of stress from the lack of nitrogen. 
The pots receiving the granules of Example 1 showed a consistant green 
color and growth, although the initial growth was slower than that of the 
surviving urea treated blades. After six and eight weeks the pots 
receiving the granules of Example 1 were green and the growth rate of the 
grass in the pots was near steady and still increasing slightly. 
EXAMPLE 3 
This example illustrates the efficacy of the high integrity natural 
nitrogenous granules prepared in Example 1 as a controlled release animal 
feed protein supplement. 
Tests were made on the comparative ammonia release in rumen fluid between 
the product of Example 1 and urea. Rumen fluid was withdrawn from a 
fistulated Hereford steer which had received no protein for 24 hours prior 
to removal of the test rumen fluid. Control and test samples were 
prepared, buffered and diluted to a total nitrogen concentration of 2500 
micrograms per milliliter and 5 milliliter samples were placed in a 
fermenter at 38.degree. C. using four replications of each sample. The 
conversion of the nitrogen into ammonia by the rumen fluid was measured by 
analyses, initially, after 30 minutes, and after 210 minutes. With the 
urea the ammonia contents in those analyses were 17, 360, and 1400 
micrograms per milliliter, indicating rapid degradation of the urea in 
rumen fluid. With the product of Example 1, the ammonia contents, 
initially, and after 30 and 210 minutes were 20, 75, and 250, 
respectively, indicating a gradual and safe digestion of the natural 
nitrogenous granules of Example 1 by animals. 
EXAMPLE 4 
This example illustrates the method of preparing high integrity natural 
nitrogenous granules for fertilizers under basic conditions, forming 
granules in an effective mechanical means, neutralizing, heating the 
granules until they harden, and drying. 
A steam jacketed Littleford FM-130 Mixer having a diameter of 24 inches and 
a length of 30 inches was used in this example. The mixer was used as a 
horizontal stationary granulating cylinder. It contained two mixing 
elements mounted on a central shaft, rotating at a peripheral speed of 725 
feet per minute, with each mixing element arranged to throw the cylinder 
contents toward the center of the granulating cylinder and force axial and 
radial flows simultaneously on the contents, creating a mechanically 
fluidized bed. The mechanical fluidization was improved and granule size 
was controlled by a single three-bladed 6 inch diameter chopper extending 
through the cylinder wall 6 inches toward the center of the cylinder, 
operating between the two mixing elements at a blade peripheral speed of 
5400 feet per minute. Fluidization was further improved by applying air 
through the bottom wall of the horizontal cylinder to produce an upward 
linear air flow rate of about 1 foot per second. 
To the horizontal stationary granulating cylinder was charged poultry 
feather meal amounting to 72 pounds with analyses by weight percent listed 
as follows: nitrogen, 12.8; phosphorous pentoxide, 1.6; sulfur, 1.6; 
potassium oxide, 0.4; and moisture, 8.0. Also added was 3.5 pounds of 
sodium hydroxide and 3.5 pounds of water. The materials were mixed, 
fluidized and heated by operation of the granulating cylinder initially 
with direct injection of steam into the mixture to secure quick heat, and 
further heating through the steam jacketed wall of the cylinder, so that 
an internal temperature of 78.degree. C. was achieved in five minutes and 
pH was measured to be 9.8. Analyses showed that 21 percent of the nitrogen 
of the poultry feather meal was now water soluble. After holding the 
poultry feather meal for 18 minutes at about 78.degree. C. it developed 
adhesive properties and formed into nearly spherical granules. The 
granules were neutralized, as a 10 percent water mixture, to a pH of 7.4 
by adding phosphoric acid. Temperature was increased to 84.degree. C. and 
the granulating cylinder continued to operate in a fluidized manner for 12 
minutes and the granules formed were hardened sufficiently to flow freely. 
The apparatus was shut down and the granules were discharged through a port 
in the bottom wall of the horizontal cylinder, to a fluid bed dryer 
operating with an air discharge temperature of 93.degree. C. The granules 
were dried in the fluid bed dryer until their moisture content was 3.6 
percent, and then screened into two size ranges for use as fertilizers, 
fine and oversize ranges for recycle to the granulating cylinder. Screen 
analysis is listed as follows: 
______________________________________ 
U.S. Screen Range Wt % 
______________________________________ 
+5 for recycle 11.7 
-5 +10 for fertilizer use 
41.3 
-10 +25 for fertilizer use 
37.4 
-25 for recycle 9.6 
______________________________________ 
The product contained no dust and analyzed 11.9 percent nitrogen. 
EXAMPLE 5 
This example illustrates the method of preparing high integrity, low odor, 
natural based nitrogenous granules for fertilizers. 
Using the apparatus of Example 4, 62.2 pounds of composted layer waste was 
charged, containing the weight percent analysis listed as follows: 
nitrogen, 3.15; water, 68.0; calcium, 10.7; phosphorous pentoxide, 5.7; 
potassium oxide, 2.4; and sulfur, 0.8. Then, 4.0 pounds of aqueous urea 
formaldehyde concentrate, derived from 48.9 parts formaldehyde and 19.2 
parts of urea, was admixed with the layer waste. Also admixed were 23.1 
pounds of urea prills, and 7.3 pounds of soluble potassium chloride. After 
mixing thoroughly the pH was found to be 9.1. The materials were heated to 
a temperature of 74.degree. C. and held under fluidizing conditions until 
the mixture developed adhesive properties and formed granules after 18 
minutes. 
Phosphoric acid, containing 62 percent phosphorous pentoxide was added in 
an amount of 2.0 pounds to neutralize the granules to a pH of 7.3 and 
heating fluidization were continued for 12 minutes more until the granules 
hardened and were free flowing. 
The granules were withdrawn from the granulating cylinder and dried in a 
fluid bed dryer at an air discharge temperature of 94.degree. C. until 
their moisture content was 3.1 percent. The dried granules were hard and 
resistant to attrition and were analyzed to indicate the chemical 
composition listed as follows: 
______________________________________ 
Component 
Wt % 
______________________________________ 
Nitrogen 
15.5 
P.sub.2 O.sub.5 
5.4 
K.sub.2 O 
7.6 
Ca 7.3 
S 0.5 
______________________________________