United States Patent (19) 11 Patent Number: 4,469,503
Stockel (45) Date of Patent: Sep. 4, 1984
54 COAL ASH FERTLIZER COMPOSITIONS 4,352,856 10/1982 Smillie .......................... 106/DIG. 1 76 Inventor: Richard F. Stockel, 475 Rolling Hills Primary Examiner-Ferris H. Lander Rd., Bridgewater, N.J. 08807 Attorney, Agent, or Firm-Sheldon H. Parker (21) Appl. No.: 481,647 57 ABSTRACT 22 Filed: Apr. 4, 1983 The invention relates to a fertilizer composition which comprises coal ash, and a relatively water insoluble Related U.S. Application Data polymer capable of gradually decomposing to slowly release nitrogen polymerized uniformly on said coal (63) Eaton-in-part of Ser. No. 54,710, Jul. 5, 1979, ash. The polymer is formed by the in situ polymeriza 3O3COCO tion of an aldehyde and a polymerizable organic nitro 511 Int. C. .............................................. C05E 11/02 gen containing compound capable of reacting with two 52 U.S. C. ........................................... 71/24; 71/28; or more equivalents of said aldehyde in the presence p of 71/29 an acid. The coal can be fly ash, bottom ash or boiler 58) Field of Search ............... 106/DIG. 1; 7 1/24, 25, slag and can be derived from anthracite, bituminous or 71/27, 28–30, 49, 61, 63 subbituminous coal or from lignite coal. The acid can be 56) References Cited phosphoric acid, the aldehyde formaldehyde and the polymerizable organic nitrogen containing compound U.S. PATENT DOCUMENTS lea. 4,067,716 l/1978 Sterrett ............................... 7 1/25 X 4,252,919 2/1981 Wagner et al...................... 7 1/27 X 27 Claims, No Drawings 4,469,503 2 1. manganese, molybdenum, copper, boron, zinc, chlorine, COAL ASH FERTILIZER COMPOSITIONS sodium, cobalt, vanadium and silicone. While all are not required for all plants, all have been found to be essen This application is a continuation-in-part of Ser. No. tial to some. These mineral elements, in addition to 54,710, filed July 5, 1979 and now abondoned. 5 phosphorus and sulfur, usually constitute what is known BACKGROUND OF THE INVENTION as the plant ash, or the minerals remaining after the burning off of carbon, hydrogen, oxygen and nitrogen. 1. Field of the Invention Each of the 20 elements play a role in the growth and This invention concerns novel, unique and useful coal development of plants, and when present in insufficient ash fertilizer compositions and a method for manufac 10 quantities, can reduce growth and yields. turing of such compositions. It has been found that by When comparing the elements of coal ash residues performing certain chemical reactions that particulate and the required elements for plant growth, it is amaz coal residue can be converted into valuable fertilizers. ing to find that only sufficient quantities of nitrogen, Depending on the specific reactions involved, the coal phosphorus and chlorine are not available in fly ash residue can be made into a slow acting fertilizer or a fast 15 residues and perhaps sufficient potassium depending on acting fertilizer and/or a combination of the two. In the origin of the coal ash. Considering the great diver addition to having present, after chemical modification, sity of elements found in nature, overlap between coal the major elements needed for growth of plants, for ash residues and what is required for effective growth example, nitrogen, phosphorous and potassium, coal ash of plants is remarkable. By suitable chemical modifica itself has present in it many of the minor and micro 20 tions to introduce larger quantities of nitrogen and nutrients needed for effective plant growth. phosphorus and small amounts of chlorine, if required, Coal is the most widely distributed fuel in the United these chemically modified coal ash residues will make States and is found in 38 states. The nation's total coal excellent fertilizers at very low cost because unlike reserves have been estimated at about 4 trillion tons, commerical fertilizers, they contain all the necessary nearly half of which is thought to be recoverable re 25 elements for plant growth. serves. The coal from the wide range of locations across Tables I and II show the variation in coal ash compo the country include fuels varying significantly with sition with coal rank and the chemical characteristics of respect to heat content, ash content and chemical prop fly ash and bottom ash from the particular coal region in erties. Coal combustion results in a residue consisting of the United States. the inorganic mineral constituents in the coal and some 30 TABLE I organic matter which is not wholly burned. The inor VARATION IN COAL ASH ganic mineral constituents, whose residue is ash, make up from 3 to 30 percent of the coal. During combustion, Chemical COMPOSITIONCoal WITH COAL RANK this ash is distributed into two parts, bottom ash col Constituent Anthracite BituminousRank,Subbituminous Percent Lignite 35 lected from the bottom of the boiler unit, and fly ash, SiO2 most of which is collected by air pollution control Al2O3 48-68 7-68 7-58 6-40 25-44 4-39 4-35 4-26 equipment. The distribution of ash between the bottom Fe2O3 2-10 2-44 3-19 1-34 and fly ash fraction is a function of the boiler type, coal TiO2 1.0-2.0 0.5-4 0.6-2 0.0-0.8 type, and whether or not a wet or dry bottom furnace is MgO CaO 0.2-4 0.2-1 0.7-36 0.1-4 2.2-52 0.5-8 12.4-52 2.8-4 utilized. Fly ash makes up from 10% to 85% of the coal Na2O - 0.2-4 m 0.2-28 ash residue and occurs as spherical particles, usually K2O - 0.2-4 m 0.1-1.3 ranging in diameter from 0.5 to 100 microns. The bot SO3 0.1-1 0.1-32 3.0-16 8.3-32 tom ash, composed primarily of coarser, heavier parti cles than the fly ash, ranges from gray to black in color and is generally angular with a porous surface. If it is 45 TABLE II collected as a slag, these slag particles generally are TRACE ELEMENTS IN COAL AND COAL black, angular and have a glass-like appearance. ASH FROMDEPOSITS AROUND THE WORLD Petrographic analysis has shown that glass is the Coal Ash primary component of ash. Other components of the Element (ppm) (ppm) ash include magnetite, hematite, carbon, mullite, and 50 Antimony 10-30 100-3,000 quartz. The major chemical constituents of ash are pri Arsenic Barium 0.8-500 2-2.57 280-10,000 18-2,200 marily silica, alumina, iron oxide, and calcium oxide. Beryllium <0.-40 1-4,000 Minor elements present include magnesium, titanium, Bismuth 0-100 0-2,000 sodium, potassium, sulfur and phosphorus. They com Boron 15-356 52-10,000 prise from 0.5% to 3.5% by weight of the ash. Ash also 55 Chlorine Chromium 30-560 <0.1-50 <0.1-7,400 contains trace concentrations of from 20 to 50 different Cobalt <0.4-34 <5-2,000 elements including antimony, arsenic, barium, beryl Copper 2.6-185 10-1200 lium, boron, copper, fluorine, lead, manganese, mer Fluorine 40-480 cury, molybdenum, nickel, selenium, tellurium, thal Gallium Germanium <1.4-100 <0.4-50 10–3,200 9-47,000 lium, tin, uranium, vanadium, cobalt and zinc. Iodine 1.11 If you compare this list of elements found in coal ash Lanthanum <1.5-40 <30-700 residues to the list of elements required for plant nutri Lead 25-3,000 200-31,000 tion, you find considerable overlap. Carbon, hydrogen, Manganese Mercury 9->5,000 0.001-300 100-22,000 oxygen, nitrogen, phosphorus, and sulfur are the ele 65 Molybdenum <0.7-200 <5-6,000 ments of which proteins, hence, protoplasm, are com Nickel 0.42->60 <5-16,000 posed. In addition to these six, there are fourteen other Palladium 0.2 elements which are essential to the growth of some Platinum 0.7 plant or plants; calcium, magnesium, potassium, iron, Rhodium 0.02 4,469,503 3 4. TABLE II-continued phate (H2PO4) and smaller amounts of the secondary TRACE ELEMENTS IN COAL AND COAL orthophosphate (HPO42). Other forms of phosphorus ASH FROMDEPOSITS AROUND THE WORLD can be assimilated into a plant, among which are pyro Coal Ash phosphates and metaphosphates. They are absorbed by Element (ppm) (ppm) plant roots. These latter materials are polyphosphates Silver 0-3 0-60 hydrolyzed slowly. Phosphorus is associated with in Strontium 0-100 0-> 1,000 creased root growth and hastens plant maturity. Potas Scandium 60-400 sium is generally absorbed as the potassium ion. The Tin Titanium <0.1-300 95-2.320 0.4-6,000 100-35,000 requirement for potassium in plants is quite high. Potas 10 sium deficiencies greatly reduce crop yields and de Uranium 0-24,000 6-1,650 Vanadium <1.4-> 100 <10-25,000 crease the resistance to certain plant diseases. Photosyn Yitrium <0.1-49 <10-2,000 thesis is decreased, thus carbohydrates are less avail Zinc Zirconium 7.6-2,000 0-140 115-21,000 0-7,000 able. Calcium is also required by high plants and it is absorbed principally as the calcium ion. Deficiency 15 results in failure of the terminal buds of the plants to It should be recognized that the diversity of the develop. Magnesium is responsible for the production chemical composition of coal ash varies from region to of chlorophyll. The chlorophyll molecule contains a region, therefore, depending on the origin of the coal, coordinated magnesium ion needed for photosynthesis. different chemical reactions should be carried out to Sulfur is absorbed by plant roots as the sulfate ion, it is obtain an efficient fertilizer. 20 almost exclusively reduced to disulfide and the mer To achieve an effective fertilizer, it is necessary to capto group. The deficiency of sulfur has a pronounced transform some of the elements found in coal ash resi retarding effect on plant growth. Boron is generally dues into a desirable chemical moieties. The major ele absorbed in the ionic oxygenated form, while iron is ments of a fertilizer are nitrogen, phosphorus and potas utilized from complex organic materials. The other sium. The known types of nitrogen containing fertilizers 25 micro-nutrients requirements are not well studied and are the following: ammonium sulfate, anhydrous ammo consequently will not be discussed. nia, ammonium chloride, ammonium nitrate, ammo DESCRIPTION OF THE PREFERRED nium nitrate with lime, ammoniated superphosphate, EMBODIMENT monoammonium phosphate, diammonium phosphate, ammonium phosphate-sulfate, calcium nitrate, calcium It has been found that functional fertilizers derived cyanamide, potassium nitrate, sodium nitrate, urea, from coal ash residues can be classified into two types. urea-sulfur, urea-phosphate, sulfur coated urea, urea The first type is where various nitrogen, phosphorus, formaldehyde, metal ammonium phosphates, for exam and sulfur organic and inorganic compounds are simply ple, magnesium ammonium phosphate, oxamide, added to the coal ash, thus these fertilizers can be con crotonylidene diurea, isobutylidene diurea, dicyanadia 35 sidered admixtures. Secondly, various compounds, ei mide and thiourea. The second major element is phos ther inorganic or organic can be made to react with phorus. There are two types of phosphorus, an organic certain chemical constituents in coal ash to form prod type and an inorganic type. The organic types are: phos ucts which are very effective fertilizers. Some examples pholipids, nucleic acids, and inositol phosphates; inor of nitrogen containing compounds which are fertilizers ganic types are collectively called orthophosphates; 40 that yield very quick available nutrients are ammonium these are phosphoric acid, superphosphoric acid, cal nitrate, ammonium nitrate with lime, ammonium ni cium orthophosphates, ammonium phosphates, nitric trate-sulfate which is a double salt, ammonium sulfate, phosphates, potassium phosphates, dicalcium phos ammonium dihydrogen phosphate, diammonium mono phates and calcium metaphosphates and the so called hydrogen phosphate, ammonium chloride, urea, a urea polyphosphates. 45 sulfur compound, a urea phosphate compound or any of With respect to the third major elements, potassium, the soluble nitrates and nitrites. Slowly available nitro you can have potassium, which is slowly available, and gen compounds are sulfur coated urea, urea carbonyl these include potassium tied up with various clay soils, compounds where the latter is formaldehyde or other or you can have water soluble potassium compounds aldehydes, metal ammonium phosphates such as magne present as potassium halides, nitrates, sulfates or double 50 sium ammonium phosphate, oxamide or calcium cyana salts containing potassium compounds. These and other mide or thiourea of dicyanamide. The nitrogen com type fertilizers containing the major elements required pounds which will form salts with the various cations for plant growth are detailed in a textbook entitled which are readily available in coal ash, such as calcium, “Soil, Fertility and Fertilizers', Third edition, by magnesium, sodium and potassium and aluminum are Samual L. Tisdale and Werner L. Nelson, published by 55 Bronsted and/or Lewis acids. Some examples are sul MacMillen Publishing Co., Inc., New York 1975. This famic, amidosulfonic, imidosulfonic, nitrilosulfonic, reference is hereby incorporated into the body of this hyponitrous, nitrous and nitric acids. Many other nitro invention. gen containing Bronsted and/or Lewis acids are also In order to have a better understanding of this inven useful. tion, it is important to understand how each of the 60 With respect to phosphorus plant nutrients, the vari major nutrient elements for plants functions. Nitrogen is ous ortho phosphates such as calcium, ammonium, po absorbed by plants primarily in the form of nitrates, tassium, etc., can be added directly to increase the con although smaller amounts of the ammonium ion and tent of phosphorus, or phosphoric acid or superphos urea can also be absorbed. An adequate supply of nitro phoric acid can be added to the coal ash residue which gen is associated with vigorous vegetable growth and a 65 will react with the cations available, the major one of deep green color. When plants are deficient in nitrogen, which is calcium. Thus calcium oxide would react with they become stunted and yellow in appearance. Phos phosphoric acid to form the various calcium orthophos phorus is generally absorbed as the primary orthophos phates. Thermal treatment of this reaction mixture 4,469,503 5 6 would form the metaphosphates, pyrophosphates and nitrogen was analyzed to contain approximately 10% polyphosphates depending on the actual reaction condi by weight. In this example, it was not necessary to tions. remove the excess water since the bottom ash particles With respect to potassium, many coal ash residues retained their integrity. This chemically modified coal contain up to 4% potassium expressed as potassium ash residue from an anthracite coal also contained about oxide. If additional potassium is needed any of the solu a % sulfur expressed as sulfur trioxide, approximately ble potassium salts could be added. Various potassium 4.2% ferric oxide, virtually no potassium oxide and soluble inorganic compounds are listed in Lange's reamining composition being silica dioxide and alumina Handbook of Chemistry, eleventh edition, edited by with some titanium dioxide present. It also contains all John A. Dean, McGraw Hill Co., New York, 1973. 10 of the micro nutrients in parts per million and in some Thus, these compounds are included as part of this cases, 10 to 50 thousand parts per million. invention. Various organic type potassium compounds could also be added, such as potassium derivitives of EXAMPLE 2 various polyfunctional carboxylic acids. Once the basic To 10 pounds of a bottom ash derived from bitumi requirements of nitrogen, phosphorus and potassium are 5 nous coal was added diammonium monohydrogen or satisfied by simple addition of compounds as an admix thophosphate. This salt has 20% available nitrogen and ture, inorganic or organic and/or the addition of com 54% available phosphorus pentaoxide by weight. Its pounds containing these elements which react with the water solubility at approximately 10 degrees centigrade coal ash, it will be noticed that the remaining major and is 57 grams per 100 milimeters of water. A saturated minor nutrients are already present. 20 solution of the salt was added to the bottom ash such These novel fertilizers comprising chemically modi that the total amount of nitrogen and phosphorus was fied coal ash residues represent a major economic im approximately 12% nitrogen and approximately 30% provement with respect to the presence of virtually phosphorus pentaoxide by weight. The bituminously every type of nutrient that a plant needs for growth. Of course, the final fertilizer composition, as mentioned 25 derived bottom ash also contained 3% potassium oxide, about 7% sulfur as sulfur trioxide and 17% calcium previously will depend on whether the coal ash is de oxide in addition to the presence of all of the micro rived from anthracite, bituminous, subbituminous or nutrients required for plant growth. lignite. Thus, if the high sulfur-potassium fertilizer is required and you do not wish, or it is not economically EXAMPLE 3 desirable, to add compounds containing these elements, 30 To 10 pounds of a lignite derived bottomash contain then the bituminous and lignite type of coal ashes are preferred (See Table I). The same is true if one wishes ing 40% calcium oxide and about 10% sulfur expressed to have a final fertilizer composition that is high in as sulfur trioxide was treated with a saturated solution calcium orthophosphate; then here too, the bituminous, of potassium nitrate commonly known as saltpeter, subbituminous or lignite coal ash residue is preferred 35 which has a water solubility at 30 degrees centigrade of over the anthracite by the addition of a phosphorus 32 grams per hundred milimeters of water. In addition, containing Bronsted or Lewis acid. In general then, a 85% orthophosphoric acid solution was added. The anthracite coal ashes are the least preferred because final chemically modified coal ash material contained approximately 7% nutrogen, approximately 28% potas they have the least content of potassium or sulfur con sium oxide and about 25% phosphorous pentaoxide, as taining residues. 40 In the following examples, no minor or micro nutri well as sufficient quantity of calcium, sulfur and the ents were added because they were present in sufficient micro nutrients. quantities in the coal ash samples which were utilized. EXAMPLE 4 Therefore, only nitrogen, phosphorus, and in a few cases potassium, were added to produce a suitable fertil 45 To 10 pounds of fly ash residue derived from an an izer. The presence of the major constituents of coal ash thracite coal was added in equal parts, monoammonium residues which are silica and alumina, are particularly dihydrogen phosphate, which contains 11% available effective carrier materials which are commonly found nitrogen and 48% available phosphorus pentaoxide by weight and dipotassium monyhydrogen phosphate in commercial grade fertilizers. In addition, these mate which rials give a loose type soil where ample aeration and 50 contains approximately 9% phosphorus pentaox excellent water drainage can occur, thus speeding up ide, 45% potassium by weight. These were added as the growth of the plant. The chemically modified coal saturated aqueous solutions. The resulting fly ash con ash residue fertilizers are particularly good for horticul tained approximately 4% available nitrogen, 20% avail tural use in nurseries where high cash value crops are able phosphorus pentaoxide and 21% available potas grown and where ornamental plants and trees are 55 sium. The fly, ash was then pelletized using potassium grown, as well as being effective for farm crops, such as silicate. . -
corn, wheat, soybean, sorgham, alfalfa, etc.
EXAMPLE 5 EXAMPLE 1. To 10 pounds of a bottom ash residue derived from a To 10 lbs. of an anthracite coal ash residue analyzed 60 lignite type coal containing 45%, calcium oxide was to contain 2% calcium oxide and 0.5% alkali oxide was treated with diammonium hydrogen phosphate contain added 85% phosphoric acid so that the final product ing 20% available nitrogen and 54% available phospho contained approximately 6% phosphorus. To this slurry rus pentaoxide by weight. The resulting fertilizer, was added urea and formaldehyde in a ration of 1.5 to 1 which had approximately 5% available nitrogen and with a minimum amount of water to form a workable 65 10% available phosphorus pentaoxide, was particularly mixture. The urea and formaldehyde under these acid good as a liming material for acidic soils. In addition, it conditions condensed to form a urea formaldehyde also had the availability of all of the micro nutrients slow release type formulation. The amount of available required for plant growth. 4,469,503 7 8 Accordingly, a suitable product can be produced EXAMPLE 6 from ten pounds of anthracte coal ash, 4.7 pounds of Using the bottom ash material treated with urea, urea and three and one half pounds of formaldehyde. formaldehyde and phosphoric acid, as described in Ex The acid can be, or include hydrochloric or nitric acid ample 1, was added tetraboric acid and potassium chlo depending upon the desired composition of the final ride, such that the resulting fertilizer is chemically product. treated coal ash fertilizer contained these important The polymerization in situ, of the urea and formalde minor elements at at approximately 1% by weight level. hyde on the coal ash carrier creates a low solubility In cases where size enlargement, for example where fly barrier between the micro-nutrient containing coal ash ash is utilized or size reduction where certain bottom 10 and the soil. Consequently, the rate of release of the ashes might be of too large a size for practical use, micro-nutrients is both decreased and correlated with methods for achieving proper size particles can be the rate of release of the macronutrients. found in the Chemical Engineering Handbook, fifth It is thus evident that the coal ash-fertilizer system of edition, by Robert H. Perry and Cecil H. Chilton, pub the instant invention is functionally superior to a mix lished by McGraw Hill Book Co., New York, 1973, 15 ture of coal ash and conventional fertilizer as well as Section E. Therefore, these methods are also incorpo clay-fertilizer systems. rated into the body of this invention. Since the coal ash functions both as a source of micro The value of using coal ash as the matrix for a fertil nutrients and alkalinity and as a macro-nutrient carrier izer lies in part in the fact that coal ash consists primar 20 an economic advantage is realized as compared to the ily of silica and alumina similar to the common materials combination of a clay carrier-macro-nutrient system and coal ash or other source of micro-nutrients and and synthetic clays used as fertilizer carriers. Coal ash is alkalinity. inert, gives bulk to the soil which allows water and air A further economic advantage of coal ash over clay to freely circulate to the roots of the plant. The coal ash as a fertilizer carrier is realized because of the wide is alkaline due to the presence of calcium and magne 25 spread distribution of available coal ash. For example, sium oxides. Since most soils are acidic, the application on the order of 600 power plant across the country of a coal ash carried fertilizer helps solve the acidity produce coal ash as a waste product from the burning of problem by partial or total neutralization of the acidity. coal. At present it is common for the power plants to The coal ash further provides the micro-nutrients re pay for the disposal of this waste material. The produc quired for plant growth. Thus, coal ash matrix fertilizer 30 tive use of this material converts a waste product which is a complete product, unlike clay matrix fertilizers. presents a disposal problem into a commercially valu Typical clays which are used as carriers in fertilizers able product located within reasonable distances from have been found to exhibit ion exchange properties. its ultimate region of use. Again a contrast is seen with Such a clay could have a cation exchange capacity in clay which must be shipped predominantly from the the range from a low of 3 to a high of 150, expressed in 35 southern parts of the United States to its ultimate re milliequivalents per hundred grams. The anion ex gions of use and is not a commodity which currently has change capacity can range from a low of about 4 to a a negative value. high of about 23. By way of contrast, this undesirable Another advantage in using coal ash as a fertilizer, is property is substantially absent in coal ash. That is to based on its positive contribution to the economics of say that the cation and anion values would be substan burning coal by virtue of converting a waste disposal tially 0. problem into an asset. All natural clays develop plasticity when mixed with It is thus evident that the use of coal ash as a micro water therefore tending to lump or agglomerate. Gran nutrient source and macro-nutrient carrier provides ular coal ash residues do not possess this characteristic both functional and economic advantages over conven thus being relatively free of lumping or agglomeration 45 tional fertilizer systems. and resulting in a more efficient fertilizer carrier. What is claimed is: As previously set forth herein, the urea and formalde 1. The method of preparing a fertilizer comprising the hyde are polymerized on the coal ash carrier in order to steps of: produce a low solubility polymer and consequently a (a) mixing water, slow release fertilizer. 50 coal ash, By way of example when eight and one half pounds aldehyde, of phosphoric acid (on a 100% solids basis) is added to acid, and ten pounds of an anthracite coal coal ash, in combina polymerizable organic nitrogen containing compound tion with the minimum amount of water which is suffi capable of reacting with at least on and one half mole cient to produce a slurry, as well known in the art, and 55 equivalents of said aldehyde in the presence of said acid then mixed with a desired quantity of urea and formal to form a relatively water insoluble polymer capable of dehyde in at least about a one and one half to one ratio gradually decomposing to slowly release nitrogen, and preferably in a two to one ratio mole equivalent (b) polymerizing in-situ, said aldehyde and said poly basis, and caused to polymerize, as well known in the merizable organic nitrogen containing compound art, an essentially water insoluble, gradual decomposi 60 to form said relatively water insoluble polymer tion polymer is produced on the coal ash. The resultant capable of gradually decomposing to slowly re product is a high content source of macro and micro lease nitrogen uniformly distributed on said coal nutrients. ash, said coal ash functioning as a carrier for said It is noted that ratio of coal ash to ureaformaldehyde polymer and as a source of micro-nutrients. is not narrowly critical and can be tailored to suit soil 65 2. The method of claim 1, wherein said coal ash is fly and plant requirements in a particular region. Similarly, ash. regional customization requirements can be by proper 3. The method of claim , wherein said coal ash is selection of the type of coal ash selected. bottom ash. 9 4,469,503 10 4. The method of claim 1, wherein said coal ash is situ polymerization of aldehyde and polymerizable boiler slag. organic nitrogen containing compound capable of 5. The method of claim 1, wherein said coal ash is reacting with two or more equivalents of said alde derived from anthracite coal. hyde in the presence of an acid. 6. The method of claim 1, wherein said coal ash is 5 16. The fertilizer of claim 15, wherein said coal ash is derived from bituminous coal. fly ash. 7. The method of claim 1, wherein said coal ash is 17. The fertilizer of claim 15, wherein said coal ash is derived from subbituminous coal. bottom ash. 8. The method of claim 1, wherein said coal ash is 18. The fertilizer of claim 15, wherein said coal ash is derived from lignite coal. 10 boiler slag. 9. The method of claim 1, wherein said fertilizer 19. The fertilizer of claim 15, wherein said coal ash is composition contains up to 40% nitrogen, up to 25% derived from anthracite coal. potassium expressed as potassium oxide and up to 60% 20. The fertilizer of claim 15, wherein said coal ash is phosphorus. derived from bituminous coal. 10. The method of claim 1, wherein said acid is phos 15 21. The fertilizer of claim 15, wherein said coal ash is phoric acid. derived from subbituminous coal. 11. the method of claim 1, wherein said aldehyde is 22. The fertilizer of claim 15, wherein said coal ash is formaldehyde. derived from lignite coal. 12. The method of claim 11, wherein said formalde 23. The fertilizer of claim 15, wherein said fertilizer hyde and is reacted with at least about two mole equiva composition contains up to 40% nitrogen, up to 25% lents of said polymerizable organic nitrogen containing potassium expressed as potassium oxide and up to 60% compound. phosphorus. 13. The method of claim 1, wherein said polymeriz 24. The fertilizer of claim 15, wherein said acid is able organic nitrogen containing compound is urea. phosphoric acid. 14. The method of claim 13, wherein said aldehyde is 25 25. The fertilizer of claim 15, wherein said aldehyde is reacted with at least about two mole equivalents of said formaldehyde. seat 26. The fertilizer of claim 15, wherein said polymeriz 15. A fertilizer composition comprising: able organic nitrogen containing compound is urea. (a) coal ash, and 27. The fertilizer of claim 15, wherein said aldehyde is (b) a relatively water insoluble polymer capable of 30 reacted with at least about two mole equivalents of said gradually decomposing to slowly release nitrogen ea. polymerized uniformly on said coal ash by the in is