Controlled Release Formulation for Fertilizers

The present invention relates to fertilizers, and more particularly to a controlled release formulation for fertilizers.

Fertilizers are generally classified into two major groupings, namely, natural organic products and synthetic chemical products. Synthetic chemical product examples would be urea, ammonium phosphates, ammonium nitrates, potassium nitrates, potassium sulfates, potassium chlorides and many others. Natural organic products are typically by-products from processing of animal or vegetable substances that contain plant nutrients of value as fertilizers. Currently, three principal types of commercialized natural organic materials are activated sewage sludge, co-polymerized leather tankage, and hydrolyzed leather meal. Sludge is typically filtered off from an aeration reactor and heat dried for commercial use as a slowly soluble nitrogen source available through microbial degradation. However, because of its low nutrient value sludge is generally used only as a base for fertilizers sold particularly to the home and garden market. Various materials containing unavailable nitrogen as keratin are used to make process tankage. The principal commercial products are manufactured from leather scrap by treatment with steam under pressure. This treatment hydrolyzes the keratin to purines and amino acids which are more available nitrogen sources. A co-polymer of leather tankage and methylene urea is also available.

Controlled release fertilizers include natural organic and synthetic chemical products in which the release or availability of plant nutrients is in some way deliberately regulated so as to distribute the nutrient uptake over time. Controlled nutrient uptake can be achieved either through modification of the fertilizer product itself, e.g. reduced solubility, coating or encapsulation, or through regulation of nutrient availability by the plant, e.g. nitrification inhibitors. In general, controlled release fertilizers have the following advantages over natural organic sources. First, controlled release fertilizers provide a reduction in the nutrient losses that occur between application and uptake by the plant. Secondly, controlled release fertilizers provide for the reduction of toxicity, especially nitrogen toxicity and particularly to seedlings, caused by high ionic concentrations associated with rapid dissolution of soluble fertilizers or from the evolution of ammonia by hydrolysis of urea salts. Finally, controlled release fertilizers provide a reduction in the number of fertilizer applications necessary thus resulting in substantial cost savings.

The above advantages are particularly advantageous with respect to nitrogen sources for plants because more avenues of nitrogen loss exist than for phosphorous and potassium. For example, denitrification of anhydrous ammonia can cause volatilization losses of ammonia, and nitrogen may be removed from the root zones of plants because of leeching or other movement of these nutrients in the soil. This loss is a particular problem in porous or sandy soils, soil subject to heavy rainfall, soils with substantial ground water movement and runoff, and areas that are heavily irrigated. Also, nitrogen may become unavailable to the plant if it forms an insoluable compound in the soil.

The most common method of modifying the fertilizer product itself to provide controlled nutrient release is to control the solubility of the fertilizer. In the case of urea, such products are typically made by reacting the urea with various aldehydes to reduce the solubility of the material. For example, isobutylidene diurea (IBDU), as described in U.S. Pat. No. 3,322,528, is a condensation product of urea and isobutyraldehyde which contains about 31% nitrogen of which 90% is water insoluble. The rate of nitrogen release is a function of soil moisture and the size of the IBDU particle so that the more moisture available and the finer the particle size, the more rapid the rate of nitrogen release.

Urea has also been reacted with formaldehyde and consists mainly of methylene urea polymers varying in chain length and degree of cross linking. Nitrogen is released from the insoluble portion of these materials by microbial degradation and therefore factors such as soil moisture, temperature, pH, nutrient content and oxygen which influence the rate of microbial activity also effect the rate of nitrogen release. As with the production of IBDU, the urea actually takes part in the reaction to form urea formaldehydes.

Modification of the fertilizer product to control the amount of nutrient uptake can also be achieved by coating soluble fertilizers to meter the nitrogen release. Coatings are generally classified into one of three types. First, there are semipermeable membranes which are broken down by internal osmotic water pressure built-up by vapor diffusion. Release of the nitrogen from the soluble fertilizer is usually complete once the coating is broken. Another type of coating involves the use of impermeable membranes with small pores. In this type of coating water passes through the coating and dissolves the fertilizer, causing swelling of the capsule and enlargement of the pores. The dissolved fertilizer then diffuses through the enlarged pores in the coating. Finally, impermeable membranes without pores are utilized to coat soluble fertilizers. In this type of coating, chemical, physical or microbial action degrades the membrane material before fertilizer release occurs, and nutrient release is usually complete once the coating is degraded.

Several controlled release products use polymer coatings based on impermeable membranes with small pores to coat prilled, soluble fertilizers. Release of the nutrients can be varied by changing the thickness of the coating. The rate of release is also governed by soil temperature i.e. higher temperatures increase the nutrient release rate. One such material is a fertilizer coated with a copolymer of dicylopentadiene with glycerol ester. Nutrient release varies with the thickness of the coating which ranges between 4% and 15% of the finished product weight. Another type of polymer coated fertilizer consists of coated urea, ammoniated superphosphoric acid, and potassium chloride. In this case, the nutrients are released through microscopic pores in the capsule wall which includes a low molecular weight polyethylene.

Sulfur coated urea has also been utilized to provide a controlled release fertilizer. Nitrogen release is based upon the thickness and completeness of the sulfur coating, the soil moisture, and the soil temperature. Increased soil moisture and temperature accelerate the degradation of the impermeable sulfur coating and thus the diffusion of urea through the pores in the coating. For such products, the rate of nitrogen release is expressed as a seven day dissolution rate. The seven day dissolution rate is measured as the percentage of urea that dissolves when a 50 gram sample of the product is immersed in 250 ml of water at 37.8.degree. C. for seven days. Typically, these products have seven day dissolution rates of between 25% and 35% which indicates a rapid initial rate of nitrogen release.

As previously mentioned, controlled release of the fertilizer nutrients may also be accomplished through nitrification inhibitors. Nirtification is the process which converts ammonium ions, when applied to the soil as ammonia, by bacterial oxidation to nitrate ions. Certain materials inhibit nitrification because they are toxic to the soil bacteria that oxidize ammonium ions. For example certain pesticides and chemicals such as nitropyrine and chlorinated pyridines are toxic to the bacteria that convert ammonium ions to nitrate. Thus, these types of inhibitors delay conversion of ammonium nitrogen to nitrate by specifically inhibiting the activity of the soil bacteria.

A controlled release mechanism can also be achieved by combining soluble fertilizers with carriers such as glass, diatomaceous earth, waxes, parafins, polymers or resins. One of these products is based on formulating micronutrient ingredients with slowly soluble glass and fritted materials. These materials are made by mixing trace elements of iron, zinc, manganese, copper, boron, or molybdenum with silicates, borates, or phosphates used to make glass. The mixture is then homogenized in a smelting process and the resultant solid mass is shattered and ground to the finished product.

Another product is based on mixing fertilizer ingredients with a suitable binder to produce a highly compacted product sold as a spike or tablet.

A hydrolyzed lignosulfonate-acrylonitrile copolymer matrix providing slow release solubility to fertilizers such as urea, ammonium phosphates, ammonium nitrates, potassium nitrates, potassium sulfates, potassium chlorides and/or mixtures thereof. The copolymer matrix may be utilized with various fertilizer manufacturing processes such as granulation and crystallization systems to impart slow release properties to fertilizers produced in solid particulate forms for direct application to soil.

The hydrolysis of the graft copolymer of lignosulfonate-acrylonitrile is carried out in an alkaline environment with any hydroxyl ion (OH.sup.--) containing alkali, preferably a caustic alkali such as lithium, ammonium, potassium, calcium or sodium hydroxide, in situ directly in the fertilizer manufacturing process or in a prehydrolysis step with subsequent use of the hydrolyzed copolymer in the fertilizer manufacturing process to provide the slow release formulation. In both cases, lignosulfonate is first graft copolymerized with acrylonitrile in various loadings of 5 to 200% of acrylonitrile to lignosulfonate with 30 to 60% preferred.

In the former case, i.e. in situ formation, the graft copolymer of lignosulfonate-acrylonitrile is treated with a hydroxyl ion (OH.sup.--) containing alkali preferably a caustic alkali such a lithium, ammonium, potassium, calcium or sodium hydroxide at a loading of 10 to 200% based on copolymer solids, with 20 to 50% preferred, and either spray dried or used as a liquid. The treated material is then mixed with, for example, a 70% urea solution and heated to about 285.degree. F. to evaporate the water in the urea solution. This in situ heating hydrolyzes the lignosulfonate-acrylonitrile copolymer to a lignosulfonate-polyacrylic acid and/or amide copolymer. The molten urea containing graft copolymer is then injected as droplets to an air cooling tower where crystalline urea is formed in a matrix of solidified graft copolymer resulting in a hard prill or bead used for shipment. The hydrolyzed graft copolymer or lignosulfonate-polyacrylic acid-amide is the copolymer matrix that protects the urea to decrease its solubility and provide a slow release formulation for a urea fertilizer.

In the latter case, a prehydrolyzed copolymer is formed for later use in the fertilizer manufacturing process by treating the graft copolymer of lignosulfonate-acrylonitrile with a hydroxyl ion containing alkali and hydrolyzing it at a desired temperature for a desired amount of time to form the copolymer matrix of lignosulfonate-polyacrylic acidamide. The prehydrolyzed copolymer is either spray dried or used as liquid. This prehydrolyzed material, when added in the fertilizer manufacturing process will protect the fertilizer from rapid solubility. In a urea prill manufacturing process, the prehydrolyzed copolymer matrix is added to urea at the desired solids concentration in water, preferably 70%, prior to water removal, and then the subsequent water removal or evaporatin therefrom and injection into air cooling towers to form crystalline prill in the urea manufacturing process imparts the desired slow release properties to the urea prill. In granulation processes, the prehydrolyzed copolymer matrix may be added into the reaction tanks, the recycled fines, or directly into the granulators to obtain the slow release properties of the invention.

In either of the above two procedures, i.e. in situ or prehydrolysis formation, the graft copolymer loading on the fertilizer in the fertilizer manufacturing process is about 2 to 20% with 5 to 10% preferred.

The drawing illustrates the best mode presently contemplated of carrying out the invention.

The FIG. 1 illustrates the solubility rate of a diammonium phosphate granular fertilizer incorporating the hydrolyzed lignosulfonate-acrylonitrile copolymer matrix of the present invention and the solubility rate of a dammonium phosphate granule control in a graph of conductivity in micromhos versus time in minutes.

In preparing the controlled release formulation of the present invention, the first step is to prepare a graft copolymer of lignosulfonate with acrylonitrile. The acrylonitrile loading on lignosulfonate may be 5% to 200% with 30 to 60% preferred. 5% is the practical lower limit at which the present invention begins to protect the fertilizer from solubility i.e. increases insolubility of the fertilizer from about 10 to 20 times that of untreated fertilizer. Likewise, 200% is the practical upper limit since beyond 200% poor crystallization or granulation will occur due to the excess acrylonitrile. Also, beyond this upper limit a poor matrix will form due to an insufficient amount of lignosulfonate present in the matrix.

Without wishing to be bound by any particular theory, it is thought that the graft copolymerization theory of a lignosulfonate with acrylonitrile entails classical, radical chain (addition) polymerization mechanisms. Initiation is carried out with a peroxide to form a free radical terminus. The chain radical formed in the initiation step is capable of adding successive monomers to propagate the chain. Propagation will continue until the supply of monomer is exhausted. However, classical termination reactions of the lignosulfonate require effective new initiation of free radical sites throughout the reaction by peroxide. Also, chain transfer as well as retardation mechanisms may also be present.

As used herein, the term "Kraft lignin" has its normal connotation, and refers to the substance which is typically recovered from alkaline pulping black liguors, such as are produced in the Kraft, soda and other well known alkaline pulping operations. The term "sulfonated lignin", as used in the specification, refers to the product which is obtained by the introduction of sulfonic acid groups into the Kraft lignin molecule, as may be accomplished by reaction of the Kraft lignin with sulfite or bisulfite compounds, so that Kraft lignin is rendered soluble in water. As used herein, the term "sulfite lignin" refers to the reaction product of lignin which is inherently obtained during the sulfite pulping of wood, and is a principle constituent of spent sulfite liquor. The term "lignosulfonate" (LSO.sub.3) encompasses not only the sulfite lignin, but also the sulfonated lignin herein above described. Any type of lignosulfonate i.e. hardwood, softwood, crude or pure may be employed during the graft copolymerization step. Lignosulfonates are available from numerous sources, such as from Reed Lignin, Inc. under the trade designations "Lignosol" and "Norlig".

Acrylonitrile (AN) is a commonly available chemical having the chemical formula CH.sub.2 .dbd.CHCN. Acrylonitrile may be prepared by dehydration of ethylene cyanohydrin or acrylamide, and is available from numerous sources such as Aldrich Chemical Co. and Fisher Chemical Co.

Illustrative of the copolymerization of lignosulfonate with acrylonitrile is the following schematic reaction: ##STR1##

The following examples demonstrate the preparation of three different graft copolymers of lignosulfonate and acrylonitrile, i.e. polyacrylonitrile (PAN), in various loadings of acrylonitrile. It should be noted that the ferrous sulfate heptahydrate is a catalyst utilized along with hydrogen peroxide to initiate free radicals for the polymerization. Propagation of the chain is continued through the use of hydrogen peroxide.

The above total weight chemicals were mixed and heated to reflux temperature (70.degree.-100.degree. C.). 25% concentration hydrogen peroxide in water was added dropwise--1 ml. per 5 minutes for 3 hours and 35 minutes (total 43 mls.).

Excess acrylonitrile amounting to 5.8 mls. was distilled off for recycle.

Recovered:

912 grams total weight, 277 grams solids, pH 5.2

Viscosity at 100 rpm Brookfield=12,960 cps

Viscosity at 20 rpm Brookfield=34,600 cps

The above total weight chemicals were mixed and heated to reflux temperature (70.degree.-96.degree. C.). Hydrogen peroxide (25% concentration in water) was added dropwise (1 ml. per 5 minutes) for 3 hours and 50 minutes (total 46 mls.).

Excess acrylonitrile amounting to 1.6 mls. was distilled off for recycle.

Recovered:

692 grams total weight at 28% solids,=194 gms. solids and pH 4.7

Viscosity at 100 rpm Brookfield=305 cps

Viscosity at 20 rpm Brookfield=375 cps

The above total weight chemicals were mixed and heated to reflux temperature (69.degree.-96.degree. C.) and reacted while hydrogen peroxide initiator (25% concentration) was added dropwise (1 ml. per 5 minutes) for 2 hours and 25 minutes (total 29 mls.).

Excess acrylonitrile amounting to 3.9 mls. was distilled off for recycle.

Recovered:

878 grams at 31%=272 grams of solids, pH 5.2

Viscosity at 100 rpm Brookfield=6240 cps

Viscosity at 20 rpm Brookfield=9000 cps

Other examples are shown in Table I to illustrate the preparation of the graft copolymer (PAN) of lignosulfonate and acrylonitrile.

In an alkaline environment, PAN graft co-polymers prepared in the above manner may be hydrolyzed to give a graft copolymer of lignosufolnate and polyacrylic acid-amide (PAA) which thickens or gels depending upon the graft copolymer loading of acrylonitrile. Hydrolysis may occur at room temperature, but would take 1-2 days to complete. Therefore, hydrolysis is preferred to occur at elevated temperature where shorter periods of time are needed to complete the process. Any hydroxyl ion (OH.sup.--) containing alkaline system may be utilized to accomplish hydrolysis so long as sufficient hydroxyl ions are present to hydrolyze the cyanide group (--C.dbd.N) of the PAN copolymer to the carboxylic group (--COOH) and/or amide group (--CONH.sub.2) of the PAA copolymer. Preferably, a caustic alkali such as lithium, ammonium, potassium calcium or sodium hydroxide is utilized. For example,hydrolysis occurs, depending upon the acrylonitrile loading and the alkali loading, if the alkali and PAN copolymer are heated at 90.degree. C. for 0.5 to 3.0 hours. Also, as noted below, heating at 275.degree. F. during the urea prill evaporation process sufficiently hydrolyzes the copolymer. Thus, graft copolymers, such as those of Examples I-III, are treated with a hydroxyl ion containing alkali, preferably a caustic alkali such as lithium, ammonium, potassium calcium or sodium hydroxide, at a loading of 10 to 200% with 20 to 50% preferred based on alkali to PAN copolymer solids. The alkaline loading is dictated by the amount of acrylonitrile solids, and a sufficient amount of alkali should be used to hydrolyze the acrylonitrile. Use of an excess of alkali will merely provide a high pH product which may be undesirable for certain applications. This alkaline treated product may then be spray dried or used as a liquid during either of the following two preferred hydrolysis steps, i.e. (1) in situ during fertilizer production or (2) in a prehydrolyzed system.

In present urea prill production, urea at 70% solids concentration in water is heated in evaporators to about 285.degree. F. to remove substantially all the water. The molten urea is then injected as droplets to an air cooling tower where crystalline urea is formed as a hard prill or bead of urea used for shipment. With the present process, 5% to 20% of alkaline treated lignosulfonate acrylonitrile graft copolymer may be added to the 70% urea solution prior to heating. The heating procedure for evaporation of the water at 285.degree. F. is sufficient to hydrolyze the alkaline treated graft copolymer of lignosulfonate and acrylonitrile (PAN) to a graft copolymer of lignosulfonate-polyacrylic acid (PAA). The alkaline treated lignosulfonate acrylonitrile graft copolymer loading on urea is 2 to 20% with 5 to 10% preferred. With loading over 20% poor crystallization results, and with loading under 2% an insufficient matrix is formed which does not protect the urea for a sufficient amount of time. The graft copolymer-alkaline system is soluble in molten urea and solidifies with the urea when cooled in the air cooling tower. The hydrolyzed graft copolymer of lignosulfonate-polyacrylic acid is the matrix that protects urea from rapid dissolving and once the molten urea and hydrolyzed graft copolymer are crystallized it is believed that the hydrolyzed graft copolymer matrix serves to encase or entrap the urea providing slow release for the urea. Examples are shown in the screening method results herein where urea dissolving time has been increased from one minute, 38 seconds to about 55 minutes.

As an alternative to the in situ graft copolymer-alkaline system described above wherein hydrolysis occurs during the urea evaporation step in a prill manufacturing process, a pre-hydrolyzed copolymer can also be used with urea as well as other fertilizers to obtain the insoluble matrix surrounding the fertilizer to provide the slow release effect. In this case a graft copolymer of lignosulfonate and acrylonitrile, such as those in Examples I-III, is treated with a hydroxyl ion containing alkali, preferably a caustic alkali, such as lithium, ammonium, potassium, calcium or sodium hydroxide and hydrolyzed independently of the urea evaporation step referred to above. Preferrably, hydrolyzation occurs at 90.degree. C. for approxiamtely 0.5 to 3.0 hours depending upon alkali and acrylonitrile loading, although any desired temperature and time period may be employed. Hydrolysis of the copolymer pendant nitrile groups occurs and a lignosulfonate-polyacrylic acid and/or amide copolymer matrix is formed that is used to protect the urea from rapid solubility. The hydrolyzed graft copolymer may then be spray dried for shipment or may be shipped in liquid form, and mixed with the 70% urea solution prior to water removal. After evaporation of the water from this mixture at 285.degree. F. this system is then cooled in an air cooling tower in the above described manner to form urea prill to provide the slow release formulation. In this prehydrolysis method, PAN loading on LSO.sub.3, alkali loading, and PAA loading on urea is similar to that described above for the in situ hydrolysis process.

Illustrative of the hydrolysis of the graft copolymer LSO.sub.2 -PAN is the following schematic reaction utilizing sodium hydroxide as the alkali: ##STR2##

The following procedure is utilized in obtaining the solubility screening referred to above and reported in Tables II and III:

1. Weigh 10 grams of urea.

2. Add graft copolymer alkaline system or prehydrolyzed copolymer at the desired loading based on urea.

3. Add water to a final urea concentration of 70%.

4. Distill water and heat the molten urea mixture to 285.degree. F. in less than 5 minutes.

5. Cool rapidly to crystallize.

6. Break the crystallized mass and obtain a 0.4-0.45 gram solid piece.

7. Add the sample to 100 cc of water at 20.degree.-25.degree. C.

8. With intermittent swirling, measure the time to completely dissolve the urea. Record as solubility index.

9. Measure the pH of a 3% solution and record.

The following test results have been obtained by utilizing the above procedures. Table II represents test results utilizing the copolymer-alkaline in situ system and Table III represents results utilizing the prehydrolyzed system.

It is clear from the above Tables that urea insolubility has increased dramatically when the matrix of the present invention is employed therewith.

The hydrolyzed lignosulfonate-acrylonitrile copolymer matrix that provides the slow release properties of the present invention may also be utilized with urea as well as ammonium nitrate, potassium nitrate, potassium sulfate, potassium chloride and ammonium phosphate fertilizers produced in solid particulate form by conventional granulation methods.

For example, when conventionally producing granular ammonium phosphate, phosphoric acid is neutralized with ammonia in a series of ammoniation reaction tanks where the heat of reaction evaporates a part of the water introduced with the acid. The extent of ammoniation is controlled to yield slurry composition ranging from monoammonium phosphate to about two-thirds diammonium phosphate, depending on the grade of product desired. This slurry flows to a pugmill or blunger in which it is granulated by mixing with recycled product fines. The granules are then dried and screened to provide a product fraction and a finer recycle fraction. Recycle ratios in the order of 8:1 are required for proper control of granulation. In one variation of the process, a rotary drum granulator is substituted for the blunger. Products made in this manner contain 11% N and 21% P, predominantly monoammonium phosphate; and 16% N and 21% P, about one-third monoammonium and two-thirds diammonium phosphate. Other grades such as one containing 16% N and 8.7% P and another with 13% N and 17% P may be made by adding sulfuric acid to the ammoniators, in which case the product contains ammonium sulfate. In still another variation, unfiltered extract from a phoshoric acid plant is used to produce lower grades that contain calcium sulfate.

Diammonium phosphate containing 18% N and 20.1% P is also made by a process in which phosphoric acid is neutralized with ammonia in a rotary drum granulator. Heated air and dry recycled fines are introduced in the granulator to reduce the moisture content to the proper level for granulation. The gases leaving the granulator are scrubbed with the incoming acid. The product is dried and then screened.

An alternate process for a material containing 18% N and 20.1% P also uses a rotary granulation drum. Phosphoric acid is neutralized in a prereactor with anhydrous ammonia to an NH.sub.3 :H.sub.3 PO.sub.4 mole ratio of about 1.3, a point near the maximum solubility of the system. The slurry thus produced is fed to the granulator along with recycled fines. Additional ammonia is added in the granulation step to give a mole ratio of 2, a point of minimum solubility. The excess ammonia required to drive the reaction to diammonium phosphate is recovered by scrubbing the exhaust gases with the incoming acid before it is fed to the prereactor. The product from the granulator is dried and screened. In addition to the material containing 18% N and 20.1% P, a large variety of grades rich in diammonium phosphate can be conventionally produced by neutralizing with ammonia-ammonium nitrate solutions rather than anhydrous ammonia, substituing sulfuric acid for part of the phosphoric acid, or adding various solid fertilizer ingredients to the ammoniator.

The following test results have been obtained by utilizing the hydrolyzed lignosulfonate-acrylonitrile copolymer matrix that provides the slow release properties of the present invention with potassium sulfate, potassium nitrate and potassium chloride. In the following Table IV, the initials "SRC" stand for "slow release compound", namely, the copolymer matrix.

The following procedure is utilized in obtaining the hardness or crushing strength data referred to above and reported in Table IV. In this procedure the fertilizer being tested is melted, slurried or dissolved in a small metal dish. A predetermined amount of the "slow release compound" or copolymer matrix is added and the two are thoroughly mixed to form a consistent mixture or solution. The system is then cooled and dried, giving crystal plates or granules suitable for crushing. These plate or granule segments are crushed using an Acme Penetrometer to obtain a measure of the relative crushing strength of the various conditioners. The penetrometer is used with a 0.1 in..sup.2 area spindle. Pounds of force are read from a gauge. Pounds per square inch crushing strength is calculated by multiplying the force figure times 10.

It is clear from Table IV that hardness and insolubility for the listed fertilizers has increased dramatically when the slow release compound or copolymer matrix of the present invention is employed therewith.

Referring now to FIG. 1, the solubility of diammonium phosphate granules including 5% of the hydrolyzed lignosulfonate-acrylonitrile copolymer matrix is compared to the solubility of diammonium phosphate granules control without the copolymer matrix. The solubility rate was measured by measuring the increase in conductivity of a granular solution of each fertilizer. The conductivity data shows a significant increse in solubility time for diammonium phosphate granules with the copolymer matrix over that of the control diammonium phosphate granules. For example, at 15 minutes the conductivity of the former is about 500 micromhos while the conductivity of the latter (the control) is about 1600 micromhos. Thus, it is clear from FIG. 1 that ammonium phosphate insolubility increases dramatically when the copolymer matrix of the present invention is employed therewith.

Ammonium nitrate may be conventionally produced in granular form substantially as described by the above processes by initially starting with the neutralization of nitric acid with ammonia in the ammoniation reaction tanks. Urea may also be produced as described above in solid granular form rather than by the previously described prill process by initially starting in the reaction tanks with carbon dioxide and ammonia through ammonolysis or from cyanamide by hydrolysis. Similarly, potassium nitrate may be conventionally produced in granular form from potassium chloride and sodium nitrate while ammonium phosphate may be conventionally produced in granular form from ammonia and phosphoric acid.

In any of the above fertilizer granulation processes, it is preferred to prehydrolyze the lignosulfonate-acrylonitrile copolymer for later use in the granulation process. The prehydrolyzed copolymer may be incorporated in the granulation process in the reaction tanks, in the recycled fines, or directly in the granulators. Preferably, the hydrolyzed copolymer is incorporated in the recycled fines and is sprayed onto the particles within the granulators where it aids in building the size of the granules being formed therein and causes the granules to become encased in the matrix of the hydrolyzed copolymer. The solubility of the resultant fertilizer granules is decreased to thus provide a slow release formulation for the fertilizer granules.

A slow release formulation has been described w;hich comprises a hydrolyzed lignosulfonate-acrylonitrile graft polymer matrix capable of giving slow release solubility to fertilizer. The hydrolysis to the graft copolymer lignosulfonate-acrylonitrile may be carried out in situ during the fertilizer manufacturing process or in a prehydrolysis step with subsequent use of the hydrolyzed copolymer with the fertilizer in the fertilizer manufacturing process.

Various modes of carrying out the invention are contemplated as being within the scope of the following claims particularly pointing out and distinctly claiming the subject matter which is regarded as the invention.