DE1592751A1 - Improved Fertilizer Mixtures and Methods for Making the Same - Google Patents

Description

P 1? 92 751.2 /

? Dr. P / T

O.M. Scott & Sons Company, Marysville, Ohio, V.St.A.

Improved fertilizer mixtures and methods of making the same

The invention relates to improved fertilizer mixtures and a method for making the same. The fertilizer mixtures can be formulated to range from a primarily high nitrogen fertilizer to a "complete fertilizer ¹¹ " and are particularly suitable for use on lawns and the like.

The term "complete fertilizer" is mainly used in technology used to denote a misogyny that contains the three main plant nutrients, namely nitrogen, Contains phosphate and potassium. When fertilizing lawns, a proportionally high nitrogen content is advantageous, and it was found desirable, a large amount To supply nitrogen during the growing season, to maintain growth and maintain the color of a well-kept lawn.

For most cultivated crops, it is possible either to add the fertilizers before planting or to treat the plants on the spot after they have grown. The usual method of applying solid fertilizers to rastn is that of most other crops

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unlike. The application is necessarily via the the foliage covering the plants and the soil made in the same way. Duroh the application method must be inorganic Salts, such as ammonium sulfate, ammonium nitrate, Calcium phosphate, chloride or sulphate of potash, separates or added in a complete fertilizer mixture with great care, so that no severe damage to the Lawn enters. The nitrogenous salts used in fertilizers with a high nitrogen content in larger quantities are required are the most harmful. The damage that results from the drying out of the grass leaves will be commonly called incineration. The inorganic salts of nitrogen are all very soluble, so is nitrogen is available to the plants almost entirely immediately, and they yield accelerated almost immediately after application Peak growth. The soluble salts are also very easily leached and lost in the process. In an attempt to do this to avoid unpleasant properties of inorganic salts, natural, treated organic substances, such as soybean meal, cottonseed meal, processed leather waste, animal residues, poultry manure, sewage sludge, used separately or in combination with the organic salts. However, this was only partially successful

The organic substances must first undergo a bacteriological decomposition in order to release uraAen nitrogen. this goes very slowly and not at all in cool weather conditions, very much in hot weather conditions accelerated relationship. It may be the case that the nitrogen is not available in cool spring and autumn weather is, but it is almost at the same speed as the inorganic salts during hot, feuohten Weather available. The decomposition is often so rapid that

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Effects are achieved, the so-called inorganic Salts are the same.

Attempts to improve uncomfortable physical properties of compound fertilizers, including caking, poor flowability or separation, have led to the development of granulation processes. The usual procedure for granulating fertilizers consists in adding 10 to 20 56 water, either directly to the dry ingredients or as part of the liquid ingredients to form a paste or slurry to build. The mixture is kneaded in wing mixers or mixed, then rolled or rolled in granulator * «to make the mixture into spherical granules in -6 + 40 sieve areas of particle size with high density to compress. In some processes these granules are dried in order to remove excess moisture. These products are in an ideal physical state for use in many stages of agriculture, but due to the particle size and density they can be difficult in the typical Apparatus used for treating lawns. Furthermore, the larger particles tend to get into the The leaves of fine lawn grasses seize and cause burns.

It has been found that the condensation product of urea and formaldehyde when it is under the right conditions was an excellent source of nitrogen forms in slowly soluble and slowly available form, the nitrogen being present in one concentration which is sufficient to allow the use of such a product as a nitrogen source for a fertilizer mix to use with high nitrogen analysis. The condensation products can in the presence of water-soluble fertilizers

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Medium ingredients are formed, and so form a resin coating around the ingredients to keep them for longer To make time available. The resin is used either alone or in combination with other fertilizer ingredients dispersed in the empty space of a carrier material, such as particles of foamed vermiculite or perlite, which continues the slow one. Release of the active ingredient improved over extended times.

The main purpose of the present invention is therefore to create fertilizer mixtures which are effective Suitable for use on lawns without "burning" or other harmful effects. These mixtures consist of the condensation reaction product of urea and formaldehyde, either coated alone or in combination with other fertilizer components on the surface of or impregnated in the pores of a silica-containing carrier material, such as foamed perlite or vermiculite for slow release of the agronomically available components for a long time. A related purpose is to create fertilizer mixtures, which have substantially homogeneous particles that are free flowing and a novel phosphorus-potassium fertilizer ingredient for UF fertilizer mixtures to create which one from Phosphoric acid and a potassium-containing component combined and with ammonia a dry, free forms flowing, granular product, which preferably has a pH of 3 »5 - 7.0.

Another purpose of the invention is to provide a complete fertilizer mixture with a particularly high percentage of insoluble and available nitrogen, the Nitrogen and the other fertilizer ingredients over

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released slowly for a longer period of time, so that a continuous fertilization is given.

Another purpose of the invention is to provide a fertilizer mixture in which a slow soluble formaldehyde resin, which has a high percentage of insoluble but • available nitrogen, impregnated between the layers of mica flakes of vermiculite or other suitable carrier materials to make the resin less susceptible to leaching.

Another purpose of the invention is to provide a fertilizer mixture in which all solid components, including soluble phosphorus and potash, are coated with a partially soluble resin to slow them down to make it soluble and so reduce the risk of burns to a minimum.

Another purpose of the invention is to provide a fertilizer solution with a leiohter, crumbly structure and lower To have a density that is much easier to handle, wherein a suitable urea-formaldehyde resin for agglomerating foamed / s carrier material with a Properly used with diohten materials, such as triple superphosphate and chloride of potash.

Other purposes and advantages of the invention will become apparent from the following description in conjunction with the appended Drawings eriiohtlioh. In the drawings is:

Flg. Figure 1 is a schematic view of one form of device to carry out the continuous process of discovery,

Figures 2, 3 and 4 are graphs showing the results

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wMerge that with products according to the invention be obtained, sioh Pig. 2 on example

VII relates and the Pig. 3 and 4 on example

VIII refer,

Fig. 5 and 6 greatly enlarged sketches showing the cross-section a particle of foamed vermiculite before and after impregnation with fertilizer ingredients demonstrate.

According to the invention it has been found that an excellent process for producing a granular "complete fertilizer" mixture with slowly soluble components can be carried out if the condensation product is an aqueous Solution of urea and formaldehyde is used to coat particles of other constituents and too agglomerate. For this purpose, urea and formaldehyde are used in aqueous solution under alkaline conditions reacted to obtain a solution containing mainly urea and formahehyd in the form of Contains methylolureas. This solution is then on dispersed a carrier material of appropriate size, such as on hemmed vermiculite alone or with properly adjusted, acidic fertilizer ingredients, and is heated in a misoher and trookner to get the To promote condensation reaction of the soluble methylolureas. During the condensation reaction, the Methylolurea solution is converted into solid, resinous methyleneurea compounds that have a high degree to have insolubility.

The ratio of urea to formaldehyde should be im Ranges from 1: 1 to 3: 1 are held, but one will Molar ratio of 1.6: 1.0 to 2.4: 1.0 is preferred in order to generate a nitrogen reaction, which the stronger

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has desired properties of 1/3 to 1/2 insoluble nitrogen, with the insoluble nitrogen having a desired level of availability. During the dissolving stage, the pH of the solution should be kept between 7.0 and 9.5. The temperature of the solution during the dissolution of urea and the main reaction phase is preferably kept in the range from 30 to 60 ^° C. in order to facilitate the dissolution of the urea and to accelerate the reaction of urea and formaldehyde. To maintain the temperature of the reaction mixture, either hot water or steam circulating through jacketing can be used.

It goes without saying that instead of using of all urea in solid form also as a solution of urea or as an alkaline solution of May use urea and formaldehyde which when combined form soluble methylolureas. These Solutions are commercially available and can easily be replaced with at least a portion of the urea solution to build. The formaldehyde can also be used either in the gas phase or as a 37 # solution, or it can be supplied in whole or in part by the commercially available urea-formaldehyde solutions will.

To get a product with a desired ratio of availability of nitrogen for plant assimilation produce, the finished product must have a pH of 4.5 or above. But if the pH of the product is higher than 6.5, the condensation proceeds less satisfactorily, and the nitrogen content is for the

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Planting is more readily available than is desirable. It has been found that ^it can be used mixing with proper selection of the components modified forms of phosphate compounds having a minimum concentration of 5 # ^ p ^ 5 ^ to the product at various pH levels within the range 4.5 to 6.5 to buffer.

Di-calcium phosphate or phosphate materials such as triple superphosphate, superphosphate, and phosphoric acid modified with alkaline materials such as ammonia and hydrated ^{quicklime have been found useful} as a source of £ p ^ 5 g and also to buffer the fertilizer mix. From the standpoint of efficient and economical operation, as well as controlling good pH, it has been found advantageous to use triple superphosphate or superphosphate treated with anhydrous ammonia. For even greater effectiveness and control of quality consistency, however, it is preferable to use a granular phosphate-potassium-containing material, which is described in detail below, to supply all or most of the phosphate or potassium, and also, to regulate the pH.

Aqueous ammonia or various ammonia-containing solutions can also be used provided that that they do not contain so large an amount of acidic ions that they prevent the achievement of the desired pH value. When anhydrous ammonia is used to add ammonia to triple superphosphate, such as in one TYA-type ammoniator, the product obtained will have desirable physical properties for use in the process. The product mixed with ammonia can

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be cooled to room temperature, or it may be advantageous in the delivery temperature of the Ammoniators of approximately 130-150 ⁰ C are used to promote the condensation reaction of urea-formaldehyde when it is incorporated with the other ingredients.

According to the invention, products with high nitrogen analyzes or crumbs or granules with light weight can be used can also be produced without the use of phosphate fertilizer material. This is achieved by using an inorganic Acid, such as sulfuric acid, which is preferred, directed as a spray onto the methylolurea solution or in the stream is introduced when sprayed onto the selected grade of vermiculite. It was found, that acid can be added in sufficient quantity to keep the pH of the solution in a range from 3.0 to 4 »0 adjust to accelerate the condensation reaction, the resulting mixture slowly through the vermiculite is buffered to the desired pH range of 4.5 to 6.5. The selection of vermiculite with proper chemical Properties and within the desired pH range is important.

A preferred vermiculite has a pH of about 6 with the following chemical analysis:

SiO ₂ 40 1 * MgO 22 i, Al ₂ O ₃ 15 - 18 years Fe ₂ O ₃ $ 10 K ₂ O 5 - 8 years CaO 1 i * Cr20, wenleer a

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Mn ^ O. less than 1 56

P ₂ O ₅ lane

S track

Cl less than 1 Ί »

HgO less than 1 56

The details of the present invention can be better understood with reference to the system of accompanying drawings, the drawings depicting typical examples of machining, to which the invention is not limited target.

Pest urea is added from the synchronized hopper 1o for batch through a continuous, gravimetric feeder, designated 12, such as a Jeffrey Waytrol feed device, and formaldehyde and water are continuously supplied by metering pumps H and 16 to a series of jacketed vessels 18 and 20 supplied. The gravimetric feed device and the Hess pumps are set so that the proper amount of the desired reactants are dispensed in a given time. The temperature of the solution is very well controlled by hot water or steam circulating continuously through the jacket of the reaction phase. A caustic solution such as sodium carbonate or sodium hydroxide etc. is added from a tank 22 through the measuring pump 24 to the reaction vessel 18. The addition of the solution is kaustisohen duroh automatic Kontrollvorriohtung 26 well controlled in order to maintain the pH value of the solution in the range of 7.0 to 9 _t. 5 The overflow from the first reaction vessel 18 is passed into the following reaction vessel 20. The number or size of reaction vessels required to obtain a satisfactory solution and sufficient residence

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time for the reaction of urea and jormaldehyde see below create depends on the speed of production Concentration of the solution and the heating power of the syteβ away. A series of two to four reaction vessels was made found satisfactory for proper dissolution and reaction in a "continuously fed system". The implemented solution, which mainly consists of There is methylolurea, is by a measuring pump 28 led to a wing misoher 30 bit double axis and casing, which by means of steam or hot Water can be heated. The addition of an acidic solution from the tank 32 by a measuring pump 34 to the urea-formaldehyde solution by a spray jet prior to dispersion on the solid fertilizer ingredients is optional if a product is to be made that contains a phosphate buffer. If desired, the acid can be added directly to the mixer 30 in an amount that adjusts the pH of the resin solution to a range of 3.0-4.0 to initiate the condensation reaction.

Pein of crushed, foamed vermiculite and the Usual fertilizer tea components, selected accordingly the desired fertilizer composition and which include chloride of potash, dolomite or the like, Superphosphate or triple superphosphate, are continuously at predetermined flow rates from the containers 36, 38, 40, 42 and 44 by conventional gravimetric » Feeding devices to the conveying means 46 and 48, which lead them to the bodice 30. Of the Yermiculite buffers the finished product to the desired pH range of 4.5 - 6.5 · As stated earlier it goes without saying that if materials such as triple acid superphosphate or phosphoric acid are used in the formulation

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be used, these with ammonia solutions, quick lime or sodium carbonate (soda ash) or other suitable substances must be modified to the desired to reach the pH range. Vermiculite alone does not have the buffering capacity necessary for a substantial percentage of triple superphosphate or the like is required.

The triple superphosphate is first fed by means of a continuous grav! Metric feed device, the at 47, fed from the container 44 to a continuous ammoniator 50 of the TVA type. Anhydrous Ammonia becomes a pressurized ammoniator under pressure at a precisely controlled rate Differential measuring cell (not shown), the pneumatic Valve 52 controls, supplied. After treatment with ammonia, the phosphate is thrown through the conveyor fed to the paddle misoher 30 along with the other selected fertilizer solids and vermiculite. The urea-formaldehyde solution is with or without the addition of acid on the fertilizer ingredients and the Vermiculite is dispersed through spray nozzles while it is agitated in the stirrer. Some of the smaller fertilizer solids will be carried away by the resin solution between the vermiculite flakes, but most will get with the resin coated on the outer surface of the vermiculite particles, there the main part of the solids is too large to pass between to fit the rolling papers. This is shown in Flg. 5 and 6 shown, wherein Fig. 5 is a greatly enlarged section of a foamed Vermlculiteohens, the very general is denoted by 100 and cavities 102 pass through its entire body. Fig. 6 shows the part 100, wieyes after coating and impregnating the resin solution

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with the fertilizer!. ingredients looks like this and shown by the blackened file 104.

The reaction that takes place in misoher 30 is exothermic. This reaction can be assisted by heating the solid constituents to a temperature of 150 ⁰ O before they are introduced into the misoher. But on each pail the components should be at a temperature of at least 15 ^° C. Actual heating of all components is not necessary since, for example, the heat from the reaction of the ammonia treatment of the triple superphosphate can be used, as can the heat from the process of foaming the vermiculite, as described below.

NaOH mixing the agglomerated product of the Misoher 30 having a temperature of about 25 is - 60 ⁰ C duroh the conveyor device 54 brought to a continuous Fördertrookner 56, and with a drying temperature of about 121-135 ⁰ C in the first zones and 95 - 100 ⁰ C to be processed in the last Trookenzonen towards the end of the ejection. The höohste temperature reached by the product during the Trooknens is about 100 -105 ⁰ C, and for the Trooknen are approximately 10 minutes erforderlioh. The condensation of the resin is terminated in the conveyor dryer 56 and the product is dried to a humidity of 2.6, whereupon the first Breoher 58 break the Breoherkuohen into pieces ranging from Kluapen from approximately 1 inch in diameter to the relevant product size of -10+ 70 mesh, which is brewed by a conveyor 60 to an elevator 62 which feeds a series of screens 64, such as a 48 inch diameter "SWECO" screen. The too big

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-H-

Particles are passed through slide channels 66 or through a common collecting belt (not shown) to a grain mill 68 brought, whereupon the particles are reduced in size and through the elevator 62 to the Seven 64 are returned. Depending on the composition of the product, 20 - 70 56 of the dryer output will be returned to the mixer 30 by a continuous feeder 70, the duroh sliding troughs with the sieves 64 and a conveyor belt arrangement 72 is connected. After sieving, the finished product is passed through the elevator 74 to a series of Packaging containers 76 brewed.

The basic, converted formaldehyde solution, which contains methylolurea, can be dispersed on the acidic solids in mixer 30, about 20-70 $> of the dry and sieved product being used as recycle material in order to achieve a favorable ratio of liquid to solids in the misoher to accomplish. An acidic solution can be added as a spray from tank 32 which will meet the methylolurea solution as it is sprayed onto the solids. The methylolurea solution can also first be mixed with the acidic solution in a pump, for example a M0YN0 ^M pump, as described in US Pat mixed solution over a length of flexible hose, with partial condensation which forms a slurry or oremige paste before it is dispersed on the other fertilizer ingredients. Although sulfuric acid is preferred, other acids such as phosphoric acid, nitric acid, hydrochloric acid, formic acid and the like can be used or solutions of acidic salts, such as acidic

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Sodium pyrophoephate, used to make the Catalyze condensation reaction.

an end product with the desired physical To produce properties it has been found advantageous to sift all solid raw materials so that they pass through a -14 mesh (US standard) Hindu sieve, and so that approximately 90-95 # a -20 mesh sieve happen. The triple super phosphate for container 44 intended to be sifted and ground for -20 mesh to get the greatest ammonia treatment effectiveness and to get the best results when incorporated into a complete fertilizer mix.

It is important to have variable addition points for both dry solids, Resin solution and return material, to create, The premixing of the dry pest components can be done in this way carried out in the same mixing device. The physical properties of the final product can be up to can be controlled to a certain extent by setting variable addition points for the resin solution and the Rüokführgut be created. The acidic fertilizers! Components along with heat provided by steam injected into the mixture, heat that fed to the mixer by means of helssem water through steam jackets will, and the pumping dryer with flow through cause the methylolurea to undergo a condensation reaction and so the desired, solid, resinous Me thylenhametof forms compounds. The condensation is introduced into the mixer and completed during drying.

The condensation products obtained act as binding agents

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medium to the smaller parts and plague components to stick together and to coat these particles with partially insoluble, resinous films which they make available more slowly in a predetermined ratio.

In addition, a high percentage of the resin is impregnated between the mica layers of the vermiculite, as a result of which these resins become more slowly soluble and available to the plants. The type and degree of Impregnation are schematic in the sketch by Pig. 6 described above. Although it It is difficult to pinpoint specific areas of solid fertilizer components that are associated with the vermiculite because of their varying densities, it has generally been found that formulations, the 15 to 30 parts of vermiculite, 20-75 parts of urea-formaldehyde resin and 25 to 50 parts of other fertilizer ingredients (all parts are based on weight) provide excellent results. The firm ones Fertilizer ingredients can of course be omitted if desired, and various ones can also be used Mixtures are adjusted so that they are adapted to special applications by various lawns, crops, etc. are required. In general, examples of suitable fertilizer ingredients are which can be used, a) phosphate compounds, such as monoammonium phosphate, diammonium phosphate, Dicalcium phosphate, phosphoric acids modified with hydrated lime, potassium phosphates; b) potassium compounds such as potassium sulfate, potassium nitrate, potassium phosphate and kainite and c) nitrogenous materials

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such as ammonia solutions, ammonium nitrate solutions, ammonia urea solutions, potassium nitrate, sodium nitrate, ammonium phosphate and ammonium sulfate.

The foamed vermiculite can be made from vermioulite ore and is fed to vessel 36 as part of the continuous process of the invention, or it can be purchased commercially in the size and composition desired. In the flow chart of Pig. 1 a suitable device is shown for processing the Vermioulits wherein Vermiouliterz is fed from the hopper 78 through a continuous feeding device, which is designated 80 to a furnace 82 having a temperature of 982 -1093 ° C (1800-2000 ⁰ P) works to peel the vermioulite ore into the foamed vermiculite. The ohemic composition of the ore and the foamed vermiculite is almost the same, with the exception of the water content. The purpose of foaming vermiculite is to widen and improve its porosity, or the cellular state of its layers.

Hot foamed vermiculite is discharged from oven 82 and falls through slide chutes 84 with a series of Sections that are inclined in alternating directions and which are cooled with water jackets 86. The partially chilled, foamed vermiculite is dispensed from the Trookentisoh 88, such as is shown in the United States patent pen 2 137 678 is described. Stone fractions are separated on the Trookentiaoh and the cleaned, foamed vermiculite is through the elevator 90 to the Container 36 brought.

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The following examples illustrate the practice of the invention and show its results. All mesh information refer to US standard sieve.

Example I.

The ratio of the raw materials used and the characteristics of 20-10-5 (NP ₂ OK ₂ O) complete fertilizers with the results obtained will illustrate the practice of the invention.

Materials parts by weight

Triple superphosphate (46 # APA) 17.65

Ammonia anhydrous 0.68

Potash chloride 6.69

Foamed vermiculite (mesh -16 + 100) 16.35

Formaldehyde (37 # solution) ■ 24.24

Urea (45 # N) 34.39

All solid components are -20 mesh size. The triple superphosphate was first treated up to 3.2 i »N with ammonia to the finished product to buffer at a pH of 5.3. As sohon pointed out, it is desirable that the finished product have a pH in the range 4.5-6.5. Urea and formaldehyde were reacted, to create a Methylolharnstofflösung, which is then dispersed to the trookenen solid components, wherein fineness was used from -60 mesh and a 40 Rüokführprodukt i "of the flight speed of the other ingredients.

A related analysis after drying $ 2> Feuohtig-

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ity content yielded 20.4 # nitrogen, 10.25 # available P ₂ ⁰ C, ^and 5 >> 1 ^ K ₂ O. Approximately 40 5 of the nitrogen was insoluble in cold water and had a desirable level of availability when processed by Method 2 , 37, 2.38 AOAC, 8th Edition, 1955, Nitrogen Activity Index of Urea Formaldehyde Compounds.

Sieve analysis of these products showed approximately $ 92> in the -IO + 40 mesh range. Less than 2 fd were -70 mesh. Sieve analysis of the dry solids prior to agglomerating with methylene urea resin found greater than 50 56 in the undesirable -40 range.

Hygroscopic properties were determined by exposing samples of the product to various steam pressures over sulfuric acid solutions and these showed a relatively low hygroscopic tendency. This product absorbed 8? £ moisture at 85 Ί "relative humidity for 24 hours at 20 ⁰ C 25 compared with 20 i" absorption at granular fertilizer products trade.

The outstanding flow properties of the condensation products of urea and formaldehyde at relative high moisture levels compared to other fertilizer materials are known. There is little inclination present for caking when under a pressure of 15 p.s.i. at a moisture content of 2 - 8 $ 6 in a bomb-type testing device was tested. Agricultural studies on burning and availability have indicated that a

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Mix approximately 3 lbs. Nitrogen, 1.5 lbs. P-Oc and 0.75 lbs. KpO per 100 sq.ft. contains, on trookene, lush lawn can be applied without damaging, while a direct mechanical mixture of urea, Formaldehyde resin, triple superphosphate, chloride of potash and vermiculite among the same Concentrations burned the lawn very heavily in 1/6 amount. Hence shows the use of the methylene urine off coating to agglomerate the fertilizer components with vermiculite to make them available more slowly by using a partially insoluble one Resin film are coated, which is partially impregnated between the vermioulite flakes, clear the Effectiveness and usefulness to minimize the tendency of the mixture to burn.

In addition, the weight of cut grass and observations of manured turf grasses make it clear that the fertilizing effect of the product is almost twice as great as that obtained with mixtures which contain more soluble forms of nitrogen.

Example II

The following recipe is an example of the ratio of raw materials used when dicalcium phosphate used to make 20-10-5 fertilizers. The results were essentially the best η as in example I.

Materials by weight

Dicalcium phosphate (365ε ΑΡΑ) 18.58

Potash chloride 6.69

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Foamed vermiculite 15.62 Formaldehyde (37 # solution) '24.24 Urea (45 1> N) 34.88 Example III

The following recipe is an example of the ratio of raw materials used when modifying triple superphosphate with quicklime (Ca (OH) ₂ ) to produce a 20-10-5t. The results were essentially the same as those of Example I.

Materials by weight Triple superphosphate (46 # APA) 17.65 Quick lime (Ca (OH) ₂ ) 1.10 Chloride from Pottasohe 6.69 Hemmed vermiculite 15.44 Formaldehyde ( $ 37 solution) "24.24 Urea (45 $ N) 34.88 Example IV

The following recipe is an example of the ratio of raw materials used when modifying triple superphosphate with soda (Na ₂ CO,) to produce a 20-10-5 D. The results obtained were essentially the same as those of Example

materials

Triple superphosphate (46 1 » APA) Soda-pure (Na ₂ CO,) chloride from Pottaiohe

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Parts by weight 65 17, 75 0, 69 6,

Hemmed vermiculite 15.79

Formaldehyde (37-6 solution) 24-, 24

Urea (45 # N) 34.88

Example Y

An example of an immediate nitrogen product, in which sulfuric acid was used to start the condensation reaction to catalyze the aqueous solution of urea and formaldehyde, the foamed Vermiculite acts as a buffer to adjust the pH of the mixture to the right value, is used as an example given for a product that can be produced according to the invention.

Materials Gewiohtstelle

Urea tablets 42.01

formaldehyde (37 # solution) 30.21

Hemmed vermiculite (mesh -16 + 100) 27.78

As in the earlier process, urea and formaldehyde are used reacted in aqueous solution under alkaline conditions to obtain a solution of reaction products, which have a high percentage of methylolureas which are introduced into the misoher. Sulfuric acid is either with the methylolurea solution through or in an incident beam the stream of solution that is fed to the spray nozzles, Injected onto the vermioulite leaf or granule before dispersing. The addition of the acid catalyzes along with the heat supplied by the jacketed misoher and trookner, the condensation of the methylol

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urea solution to resinous methylene urea compounds. In carrying out this process, a part of the resin solution in the Nisoher becomes solid products condenses, the condensation in the dryer being completed. Part of the product is returned to get the desired liquid to solids ratio.

Agricultural studies on scalding have indicated that these products can be found in succulent lawn grasses a ratio of 10 lbs. Nitrogen and 1000 sq.ft. can be applied without causing harmful effects. Urea causes 1/20 of this Lots of severe burns to the lawn during hot summerweifcers. The degree of hygroscopy is very low, and there is practically no caking, even at a level of 8-10? 6, if he a pressure of 15 p.s.i. is suspended.

Example YI

To the agglomeration effect of the partially converted Urea-formaldehyde solution in the production process more homogeneous Particles to show was a sample 20-10-5 (! T-P ^ Öc-KgO) Fertilizer mixture a) produced according to the invention and b) made a mechanical mixture as a comparison, wherein the same materials were used, but the urea-formaldehyde condensation products as fine ground dry compound were subjected to sieve analysis. The results were as follows:

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U.S. Sieve J » agglomerated f> ! Dry, mechanical Product - A Mixture - B + 10 1.4 0 -10 + 20 64.2 1.7 -20 + 40 21.2 51.9 -40 + 70 8.4 50.2 -70 + 100 1.7 11.2 100 2.5 24.5

The agglomerated product has a greater percentage in the desired -10 + 70 mefeh range with no "sizeable -100 dust fraction and is homogeneous in the mix.

Example YII

To show the greater resistance to leaching through the impregnation of the urea-formaldehyde solution between layers of vermiculite mica, two identical samples of 25N-0-0 (Ν-Ρ ₂ Ος-Κ ₂ 0) product are made, namely (I. ) with the standard quality No. 4 (-16 + 100) vermiculite and (II) with No. 4 Quality pulverized into a fine powder by repeated passage through a powder mill. In addition (III) a mixture of urea and No. 4 Vermiculite with a nitrogen concentration of 25 Ί »produced for comparison in these tests. In each case a 1g sample was placed on filter paper and aeohsmaik repeatedly leached with 6 ml portions of distilled water. In each series of tests, each sample was allowed to drain well between each leaching so that virtually all of the free water was removed. In each extract, the

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Nitrogen content is determined and the cumulative percentage of total nitrogen extracted is shown in given in the following table:

Percent of total nitrogen extracted

Extract number I.
Standard parts
Vermiculite II
Pulverized
Vermiculite III
Urea-
mixture 1 8.5 9.35 77 2 19.2 25.3 92 3 27 34.6 98 4th 32.6 41.7 99 VJl 37.8 47.4 100 6th 43 52.3 100

Results of the leaching of Samples I and II are in Pig. 2 shown graphically.

Example VIII

In order to show the effect of coating ammonia-treated phosphates with a relatively insoluble urea-formaldehyde resin, a 20-10-5 (N-PgOe-Kg ⁰ ) product (I) was composed according to the method of the invention, and a product (II) was made with the same ingredients, but put together as a troubled, mechanical mixture. An Ig sample of each was leached with 9-50 ml portions of distilled water. Almost all of the free water was drained off between each repeated leaching and the extract was analyzed for PgOc.-content. The cumulative percentage of the total P ₂ Oe leached from these samples is given in the following table:

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Extract number τ 1 21.2 CVi 33.7 3 43.7 4th 50.2 VJi 52.7 6th 54.6 7th 55.8 8th 56.9 9 57.8

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II

57.3 61.0 64.1 65.3 66.9 67.5 67.7 68.3 68.9

The results are in Pig. 3 graphically shown.

The products of the same recipes were used in different proportions on creeping curved lawns upset that feuoht from during hot summer weather Dew was. The mechanical Misohung (II) caused im Ratio of 3.375 lbs. per 1000 sq.ft. a burn of 1 °, while the standard product according to the invention did not produce a full degree of burn at ratios up to 6.75 lbs. per 1000 sq.ft caused. The degree of combustion is expressed in values from 1-10, where 0 indicates no combustion and 10 indicates perfect Browning of the whole lawn or foliage. The results of different ratios of application are in the pig. 4 graphically shown. In summary, these results show the value of urea overcoating -Formaldehyde ^ to make the other constituents much less soluble and the occurrence and degree of combustion of the lawn.

Example IX

To see the effect of No. 4 vermiculite on the nose diohte of the product was a 25-0-0 (N-PgOc-KgO)

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Product (I) produced by the process according to the invention, where ZONOLITE ITo. 4 vermiculite used became. For comparison, a sample, designated II, was composed, the same Materials were used, however the No. 4 Vermiculite was pulverized so that everything passed through a 100-mesh sieve passes through. The mass density of the two products is as follows:

Mass density (loose volume)

I standard product 16.2 Lb / Cu. Pt. II product with powdered Vermiculite 22.4 Lb / gu. Pt.

One of the commercially very successful rane fertilizers was made according to the above and was used in large quantities in the USA under the trademark "Turf Builder" from The O.M. Scott * Sons Company, Marysville, Ohio, in the Trade brought. An improved design of this fertilizer and a method for making it are obtained, however, when a new, granular phosphorus-Kal ium-Vormischbe constituent with the Harn et off-formaldehyde is introduced before the condensation reaction of the latter. In some cases, for example, the use of naturally occurring superchosphate rock and the like some changes in the analysis of the finished product caused by the change in the analysis of the rock. The use of phosphate rock also limits this Phosphate analysis because of the large percentage of indifferent materials in the rock. Other impurities in the rock also have an undesirable effect Effect on urea-formaldehyde condensation product

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e.g. they make the end product slightly rubbery and less free flowing.

As discussed above, a urea-formaldehyde fertilizer is used according to the invention urea and formaldehyde reacted together under alkaline conditions to a Form solution of methylolureas. Then the Methylolurea solution either foamed with a surfactant or another suitable one Foaming agent or mixed with a porous carrier material such as vermiculite, perlite and the like. Preferably becomes the methylol solution during mixing or foaming acidified and subjected to conditions sufficient to cause the condensation reaction between the urea and to promote formaldehyde. Additional fertilizer ingredients that contain nitrogen, phosphorus and potassium can add to the nitrogen-rich methylolurea solution can be added before or during mixing or foaming. The purpose of the additional Materials is the main one to create phosphorus and potassium in the fertilizer in an amount that is suitable for favorable assimilation by the plants. However, since these substances are acidic, they can create a substantial cost saving when used to adjust the pH of the methylolurea solution to regulate during the condensation reaction and in the finished product.

According to the invention, very good, granular P-K fertilizer components are made found which are suitable for every purpose and which the fertilizer mixture in different Improve directions. The P component can be produced by adding potassium containing material, e.g.

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Pottasohe chloride, potassium sulfate, potassium hydrogen phosphate, monopotassium phosphate, dipotassium phosphate, sulfate of PottasohenmagneBium, potassium carbonate, potassium nitrate or any desired mixture thereof, can be introduced into a TVA drum-type ammoniator. Every Device which is used for bringing together granular Material can be used with a spray or a steam, but an ammoniator can be used drum type is preferred.

To this, phosphoric acid and anhydrous ammonia are added and the reaction is carried out on the surface of the potassium-containing material. The product can then be further acidified, e.g. using a mineral acid such as sulfuric acid to neutralize any free ammonia and obtain the desired ρH value, but this is not necessary. The source of phosphoric acid is preferably liquid phosphoric acid with high P ₂ ⁰ C concentration from a wet process. This has the immediate advantage over granular materials such as triple superphosphate and the like that the preparation of the fertilizer mixture is facilitated in that it is in a liquid state and can therefore be easily handled with the usual pumps and reading devices. The Pp ⁰ S concentration is preferably 54 nindestens Ί "and i 76" or more, if available to 1st.

The relative amounts of potassium salt and phosphoric acid are not critical as the final pH is preferably known in a known manner by the extent of the ammonia treatment is set, and the contents of P and K can, if

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Desired to be varied widely. Rüokführung8 material is added to control particle size and to reduce pollution of the ammoniator to support. The resulting mixture is a dry, free flowing, granular product with a pH between 3.5 and 7.0, although 4-6.5 is preferred and 5.0-5.5 is good on de is.

When producing a urea-formaldehyde fertilizer, the granular P-K mixture is also treated with a urea-formaldehyde solution and the funnel, if the latter is desired, e.g. vermiculite or perlite or with the urea and Formaldehyde alone, in a process in which the urea-formaldehyde solution is hemmed and no Hopper is desired, mixed. The resin obtained is then polymerized, dried, sieved and ground by a condensation reaction and results in a complete nitrogen-phosphorus-potassium fertilizer.

The preferred method of making the new, granular P-K ingredient is as follows: Liquid phosphoric acid is metered into one end of the ammoniator while chloride from potash can be conveniently and gravimetrically introduced in contact with the phosphoric acid. The touch of phosphoric acid with KCl creates a suitable basis which the implementation phosphoric acid with ammonia allowed. It was found, that the reaction of ammonia with phosphoric acid without the KCl a viscous mass or a gel in the preferred one pH creates which are both difficult to handle and so difficult effective through continuous fertilizer growth are to be combined into a fertilizer. AneohlJaßend will

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treated the phosphoric acid-KCl product with ammonia, preferably with anhydrous ammonia. The water present in the phosphoric acid is released by the heat of reaction evaporated with the ammonia. If desired, sulfuric acid can then be added to the ammonia treated Product can be sprayed to ensure that all free ammonia is neutralized. More available, freer Ammonia can tend to cause the condensation of urea ormaldehyde to delay. The entire process is carried out while the reaction product is in circulation to be led.

Individual examples explain the use of the granular P-K component:

Example X

Stage 1 1.2 lbs / min of potash chloride, 10.0 lbs / min of recycled material (19.60 P ₂ O ₅ * 36.57 K ₂ O, 4.23 S ^ N), 1.0 lbs / 54 min of 54 1 * P ₂ Oc of wet process phosphoric acid and 0.20 lbo / min of anhydrous ammonia were combined in a TVA drum-type continuous ammoniator. Sufficient sulfuric acid was added to adjust the pH to between 4.5 and 6.5. The substances are mixed for 7 minutes, maintaining the temperature at 121 ⁰ C (25O ⁰ P) increased. The finished product is continuously withdrawn and has the following analysis:

Total P ₃ O ₅ 25.00 56

K ₂ O 31.88 56

Ammonia nitrogen 5.57 i>

pH 4.7 #

H ₂ O 1.00 Ji

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Level 2 4.37 lbs / min urea, 2.17 lbs / min urea-formaldehyde concentrate (59 # formaldehyde, 26 # urea, 15-6 water) and 0.80 lbs / min water are combined in a vessel. The resulting solution is placed in a mixer at a ratio of 7.26 lbs / min to 1.58 lbs / min vermiculite and 2.70 lbs / min of the mixture after stage 1. The mixture obtained is polymerized, dried, sieved and ground to give a product with the following composition:

Total nitrogen

Nitrogen insoluble in cold water

Nitrogen, availability index

^P 2 ° 5 K ₂ O

PH moisture

$ 22.98> 10.72 0

54.20 # 6.92 $ 9.84 # 5.9

2.8

The above product makes a granular, free flowing N-P-K fertilizer with a slight weight and slow release characteristics and high Nutrient analysis.

Example XI

Stage 1 1.05 lbs / min potash chloride, 8.0 lbs / min recycle (24.2 P ₂ ° ₅ »32 # KgO, 5.5 1» N), 1.25 lbs / min 54 # P ₂ On wet process phosphoric acid and 0.20 lbs / min anhydrous ammonia are combined into a TVA drum type continuous ammoniator. The materials are mixed for 7 minutes while keeping the temperature

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rises to 121 ⁰ C (25O ⁰ P). The finished product is continuously withdrawn and has the following analysis:

Total P ₂ O ^

K ₂ O

Ammonia nitrogen

PH H ₂ O

28.40 * 28.44 *

5.43 Ji

5.3

1.9 f

Step 2 4.37 lbs / min urea, 2.17 lbs / min urea-formaldehyde concentrate (59 Ji formaldehyde, urea Ji 26, 15 1 x water) and 0.80 lbs / min of water are zusamaengegeben in a vessel. The resulting solution is combined in a mixer at a ratio of 7.26 lbs / min to 1.58 lbs / min vermiculite and 2.70 lbs / min of the solution after setting 1.

Example XII

Level 1 1.2 lbs / min potash chloride, 10.0 lbs / min dry material (19.60 + P ₂ O ₅ , 38.13 KgO, 4.06 Ji N), 1.0 lbs / min 54 Ί » P ₂ Oc phosphoric acid from the wet process and 0.20 lbe / min anhydrous aniDonia are put together in a continuous ammonia tor of the TVA drum type. Enough sulfuric acid is added to adjust the pH between 4.5 and 6.5. One misoht the materials for 7 minutes, maintaining the temperature at 121 ⁰ C (250 ⁰ P) increases. The finished product is continuously withdrawn and has the following analysis:

QtSaat K ₂ O

19.60 36.57

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Ammonia nitrogen

4.23 5.4

2.10

Level 2 4.37 lbs / min urea, 2.17 lbs / min urea-formaldehyde concentration (59 56 formaldehyde, 26 j6 urea, 15 * water) and 0.80 lbs / min water are combined in a vessel The resulting solution is mixed in a mixer at a ratio of 7.26 lbs / min to 1.58 lbs / min vermioulite and 2.70 lbs / min of the mixture of stage 1. The mixture obtained is polymerized, dried, sieved and ground.

Example XIII

Level 1 2.4 lbs / min chloride from potash, 1.0 lbs / min 54 ° i? 2 ^Ο 5 £ h ° ^s Pfc ^{orsäure from} a wet process, and 0.20 lbs / min of anhydrous ammonia in a continuous Ammoniator from the TVA -Drum type put together. The materials are gemisoht for 7 minutes, maintaining the temperature at 82 ⁰ C (180 ⁰ F) increases. The finished product is continuously withdrawn and has the following analysis:

Total P ₃ O ₅ 13.60 Jt K ₂ O 40.94 Ji Ammonia nitrogen 3.23 ί PH 5.5 H ₂ O 1.40 i

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Level 2 3.92 lbs / min urea, 1.95 lbs / min urea-formaldehyde concentrate (59 $> formaldehyde, 26 5ε urea, 15 # water) and 0.70 lbs / min water are combined in a vessel. The resulting solution is added to a mixer at a ratio of 6.75 lbs / min to 1.0 lbs / min vermiculite and 2.3 lbs / min of the Stage 1 mixture. The mixture obtained is polymerized, dried, sieved and ground.

step 1

Level 2

Example XIV

1.0 lbs / min chloride from potash, 6.0 lbs / min recycle (23.0 SiP ₃ O ₅ , 35.31 j6 K ₂ O, 4.46 # N), 1.2 lbs / min $ 54 P ₂ O ₅ phosphoric acid from a wet process and 0.20 lbs / min anhydrous ammonia are combined into a TVA drum type continuous ammoniator. The materials are mixed for 7 minutes, the temperature ^{rising to 93 °} C (200 ^° F). The finished product is continuously weighed and has the following analysis:

Total P ₂ Oe

K ₂ O

Ammonia nitrogen

pH

H ₂ O

25.3 27.0

5.5 5.0 + 2.0 i>

2.4 lbs / min urea, 1.2 lbs / min skin-formaldehyde concentrate (59 $> formaldehyde, 26 urea, 15 56 water) and 0.6 lbs / min water are combined in a vessel. The solution obtained is in a ratio of

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4.2 lbs / min to 1.8 lbs / min vermiculite and 3.5 Add lbs / min of the mixture to a mixer after step 1. The mixture obtained is polymerized, dried, sieved and ground to give the final product.

The invention can be carried out in other particular forms without losing its essential characteristics to deviate. The present embodiments are therefore to be considered in all respects as examples and not as limitations. The scope of the invention is evident from the attached drawings, claims in connection with the description and all changes which occur within the meaning and range of equivalency of the claims are included.

- patent claims -

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Claims (12)

PATENT CLAIMS 1. Improved fertilizer mix with a high. Content of available and insoluble nitrogen, characterized by a porous silicon-containing Carrier material which is coated on its surface with methylolurea and furthermore with it is impregnated. 2. IKingmittel mix according to claim 1, characterized in that that the carrier material is perlite or vermiculite. 3. JXing agent mixture according to claim 1, characterized in that that it also contains buffer substances. 4. Fertilizer mixture according to claim 1, characterized in that the carrier material is impregnated with condensation reaction products of a methylolurea solution which contain urea and! LiOrmaldehyde in a molar ratio in the - ^ ereiohe from 1: 1 to ^v ) χ 1, 5. Process for the preparation of a fertilizer mixture rujch one of the claims 1 to 4, characterized in that that a finely divided, porous, silicon-like carrier material with a neutral or ßlkaliöohen methylolurate solution is mixed, which urea and formaldehyde in the molar ratio in the range of 1; Contains 1 to 3: 1, 109812/1312 BATH ORIGINAL - 38 - and that the Methylolharastoffe duroh increase the Aoidity of the methylolurea solution and / or increase in the temperature of the mixture during and naoh this mieoh process in situ in and around the Carrier parts have to be converted to methylene urea. 6. The method naoh claim 5, characterized in that the methylolurea solution before or during their mixing with the carrier material by adding an acid or an acidic salt to the Methylolurea solution is adjusted to a pH in the range of 3.0-4.0. 7 * procedure NaOH any one of claims 5 or 6, characterized in that the Misohung of methylol Iösung and carrier material to a pH value in the Bereioh of 4 _t 5 Mb 6.5 is buffered. 8, method according to claim 7, characterized in, that the mixture with dicalcium phosphate, triple superphosphate or with phosphoric acid, which with ammonia, hydrated quicklime or sodium carbonate modified, is buffered. 9. The method naoh one of the preceding claims, characterized in that one or more additional Fertilizers are added to the carrier material together with the methylolurea solution. 10. Method according to one of the preceding claims, daduroh indicated that the fertilizer mixture to complete the condensation of the methylol 10981 ^ / 1312 - 39 - urea is dried to methylene ureas at an elevated temperature. 11. The method according to claim 10, characterized in that the dried fertilizer mixture by crushing is brought into a finely divided form. 12. The method according to "one of the preceding claims, characterized in that 20-70 # of the fertilizer mixture be fed back into the mixing process. 12/1312 Blank page ORlGIiNiAL INSPECTED