United States Patent [191

Stoller et al.

' 3,649,239 3,679,390

Feb. 16, 1982



3/1972 Mitchell ............................ .. 71/28 X 7/1972 Young 71/29


Inventors= Jerry H- Stoller, Bunkerlllll, ,TeXs

3,713,802 1/1973 Gittenait .... ..


Harold A- Hartung, colhngswood,

3,723,086 3/1973 Poynor 618.1.
3,918,952 11/1975 Neumiller

260/555 R



51°11“ Enterlmses’Inc-1110mm“,


2/1976 Greidinger 61 al. .
7/1977 Funk ........... ..


Snyder ............... ..

71/29 x


3/1977 Beresky et al. ............ .. 71/29 x
9/1978 Jones ........................ ........... .. 71/29 , ,

Appl' No" 119’429


[22] F?ed‘
_ _

Feb‘ 7’ 1980
Related US. Application Data

. 1481286

4/1966 France .
7/1959 United Kingdom .'

Contlnuatlon-m-part of Ser. No. 954,733, Oct. 30, 1978,
_ ........ .. 71/29, 71/64.1

969362 9/1964 United Kingdom '
1149924 4/1969 United Kingdom .


Int. 01.3 .............................................. .. cosc 9/00
U_.s. Cl. ........... ..

1182395 2/1970 Umted K311699111»
1211537 11/1970 1307828 M973 Umted Kmgdom . United Kingdom ‘


Fleld Of Search ................... .. 71/1, 11, 27, 28-30,

‘ [56]

71/119, 64 c, 64.1; 260/555 R, 555 s, 555 0 References Cited


1354784 5/1974 United Kingdom _ 1363046 8/1974 United Kingdom .

. . 3/1973 Umted Kmgdom .

U.S. PATENT DOCUMENTS 2,770,538 11/1956 Vierling ................................ .. 71/29 2,814,556 11/1957 Christoffel .. .. 71/29 2,855,286 10/1958 Harvey ..... .. 71/29 2,869,996 1/1959 Vierling .. 71/29 3,022,153 2/1962 Miller .... .. 71/2_9 3,022,154 2/1962 Potts et a]. 71/34 3,096,168 7/1963 Walters ..... .. 71/28 3,234,004 2/1966 Smith et a]. . 71/28 3,235,370 2/1966 Kealy ........ .. 71/29 3,326,666 6/1967 Walters 71/29 3,523,798 8/1970 3,527,591 9/1970 Stauter 71/28 X 3,529,951 9/1970 Every et al. .... .. 71/28 3,554,730 1/1971 3,582,311 6/1971 Browder et a]. 71/29 X 3,640,698 2/1972 Backlund .............................. .. 71/29
Kai] . . . ... .. . . . . . .. 71/29

Primary Examiner—S. Leon Bashore
Assistant Examiner-Ferris H. Lander Attorney, Agent, or Firm—Kenneth H. Johnson



High analysis liquid fertilizers comprising the reaction
product of urea and phosphoric acid having a pH be tween 1.5 and 4 and optionally containing the reaction product of urea and sulfuric acid, various trace elements including those normally found as contaminants in Wet

process phosphoric acid, potash and gelling agents, said
fertilizers being further characterized as having total analysis of N, P205 and K20 of at least 25 weight per cent and preferably 30 weight percent or greater.

Slaber et al.

.. . ... .

. _ . . ..


31 Claims, 3 Drawing Figures

16.763 H2804 93% . 1982 Sheet 10f2 4.315.S. Patent Feb.U.

315. 1982 Sheet 2 of2 4. 16.S.U.763 N+ P2 O5 1g. Patent Feb.3 .

this fact is used in British patent speci?cation No. US. In these cases. to which is added urea or ammonia plus nitric acid to furnish additional nitro gen.924 to make solid urea phosphate. the solubility and assay are apprecia bly lower. Modern agriculture is based on appropriate fertiliza tion.538 and 2. Field of the Invention The present invention relates to high-analysis low pH liquid fertilizer compositions and the methods of pre paring said compositions from phosphoric acid. advantage of the invention that these liquid fertilizers 55 are prepared autothermally. Pat. Provision of formulating ?exibility so that the de sired precise nutrient ratios can be made from a minimum number of simple components in US. In the present 25 work. stabilization with amines is required if storage periods greater than a few days are contemplated.952 uses potassium chloride. this reaction is the equimolecular reaction of urea and phosphoric acid to produce a coordination-type com plex by the equation: ' these efforts.996 describe liquid prod ucts made from phosphoric acid neutralized with am monia and potassium hydroxide. Pat. No. potash and other common agricultural materials. and much effort on the part of many investi gators has been directed at improving the cost-effec tiveness of fertilizer systems and practices. a known compound and liqui?ed urea. Solutions of higher concentration crystallize. US. Maximizing agronomic ef?ciency. Production of higher analysis compounds 2. 3. 3. made from conventional commercial materials. Dilute aqueous solutions of urea phosphate have been described.No. 3. Pat.022. liquid fertilizers are growing in acceptance because of economics in appication and placement. Pat. No. suspensions when K exceeds the limit of solubility. urea is used as the source of BACKGROUND OF THE INVENTION 1. 1978. For example.640. The products are usually neu can be easily mastered by compounders. Com plexes of urea and micro-nutrient metals are described Liquid fertilizers provide opportunities for further savings in several key areas including: 1. The reaction of urea and phosphoric acid to pro duce urea phosphate is known. or by removing contaminants from the cheaper 60 particular feature that the liquid fertilizers may be man converting orthophosphoric acid to polyphosphoric ufactured in simple equipment that is readily available and low in cost. US. Pat.S. US. US. It is a feature of the Generally in the prior art. Nos. Simpli?cation of the compounding process and equipment so that it can be moved as close as possi of low pH and‘ low analysis. Use of lowest cost components 3.713. or This application is a continuation-in-part of Ser. urea.556 shows how to combine the crystallization of solid urea phosphate described by the latter.770. Pat.. 2. giving a 20 products of higher analysis have become available. These products are clear liquids. . separating the precipitated urea-phos phate and ammoniating it to convert it into commer 6. is 90 parts per 100 parts of water by weight.7 for stability feature of the present invention that the liquid fertilizers and achievement of the required analysis. As a result of nitrogen and phosphoric acid as the source of phospho rous. or by pared from a limited number of components.315. and now abandoned. in this process.918. leading to cost reduction all along the line from the point of manufacture to application in the ?eld. at 0° C. using straight-forward precedures that acid by heat treatment. urea reacts with sulfuric acid to form urea sulfate. urea and ammonium polyphos fertilizers having high total nutrient content according to commercial standards may be prepared. especially with regard to retention and utilization of nitrogen in the cially useful grades of liquid or solid fertilizer. No. Pat. 2. 4.153 teaches the combination of urea. ammonia. It is an advantage of the present invention that liquid to produce liquid fertilizers. urea.446.086 discloses reacting merchant grade wet pro cess phosphoric acid and urea followed by ammoniation ing novel liquid fertilizers. with some 65 may be made quickly.869. wet-process phosphoric acid and ammonia.149. Incorporation of trace and secondary elements from low-cost inorganic sources phosphoric acid.733 ?led Oct. The limit of solubility of this material in water at 25° C. It is a further phate to make high analysis liquids. 3. No. The cost of acquiring and applying nutrients is dominant. The term“autotherma1ly” is used herein to indicate an exothermic reaction.S. without tion of high analysis liquid fertilizers.814. Similarly. As recognized in the art. U. It is a acid. In US. 1.640. in these products.802 a process is described for reacting urea and wet process ble to the point of application 5. Pat. 2. All of these elements have been addressed in the current invention. It is a particular advantage of the exceptions as noted above (US. reaching values of 50% or more). Pat. for example.' present in the phosphoric acid.698. The present invention utilizes a novel concept to carry these solution containing 7% nitrogen and 17% phosphorous pentoxide.763 2 of the present invention is low pH fertilizers of high total nutrient content (25% or more. ents (N+I’+K below 25%) can be realized. without recourse an exter nal heating. No. No.116.664.013. 30. 4. and what results is a novel method of produc. Urea is also reacted with sulfuric acid to make certain fertilizer grades as shown in U. The ?eld . No. high analysis liquids are present invention that the liquid fertilizers may be pre achieved by using expensive furnace grade phosphoric wet process phosphoric acid by costly processing. Pat. 3.723. potassium chloride is the only form of potash compati ble with the other ingredients.698) in present process that commercial grades of components which only low concentrations of total primary nutri may be satisfactorily employed to produce the fertiliz ers. to these may be added mod 40 erate amounts of other nutrients to form liquid systems 4. stable liquid fertilizers are produced that are far favorable factors much farther than previously possible. In the present invention. 954. separation of the urea-phosphate by precipita tion and ?ltration is required to remove contaminants soil and phosphate availability. 3. It is a further tralized to pH values ranging from 6 to 8. see. phosphoric acid and potassium chloride to make neutral liquids of high analysis containing am monium phosphate.1 HIGH ANALYSIS LIQUID FERTILIZERS 4. and relatively expensive polyphosphates must be used. Prior Art Much work has been done in the past on the produc more concentrated than the former references. No. No.

employing acid fertilizers.. have a pH of less than 4.7% N. wherein N may range up to 30 weight percent..3 4.1 mole up to about 3 moles of ‘urea per mole of acid present.. In many instances. aluminum or iron sulfates or chlorides. the so-called super concentrations of potash are obtained by liquids. and one of the advantages of urea over ammonia is that this loss is ‘ urea and a mixture of phosphoric acid and from 5 to 80 weight percent sulfuric acid based on said phosphoric acid in a mole ratio of about 0. (2) reacting said urea and said acid exothermally and greatly reduced. usu ally at least one mole of urea per mole of acid. P205 and K20 analysis of at least 25 weight % and preferably greater than 30 weight % of the fertilizer. This effect is well known. % P205 suspending the potash beyond its solubility limits in a ?nely divided form with the aid of gelling materials (viscosifying agents) such as clays (montmorillonite. % N.1 to 30 wt. % N. K20 being 0 and the N being greater than 0. the liquid fertilizers presently in wide use.5 to 2. However. which occur naturally in the phosphoric acid. 37% P205 and 0% K20 the past to increase trace element availability. izer such as zinc. 5 to 50 wt. which substantially im proves the availability and mobility of metallic trace elements. giving clear liquids which have an analysis of N. the present invention are highly acidic non-ammoniated loss of ammonia into the atmosphere is substantially liquid fertilizers. rendering the phosphate ions free and available. it is a particular advantage that the present invention allows inclusion of secondary and trace elements in stable and available form without prior-art chelated or complexed products. benotonite) heteropolysaccharides. P205 up to 50 weight percent and K20 up to 30 weight percent. up to about 3 moles of urea may be added (depending on the amount of sulfuric acid present. however.e. since up to 3 moles of urea will combine with A further most important feature of the present in vention is to provide fertilizers of improved agronomic ef?ciency. % K20. urea is converted to ammo 40 nia by decomposition in the soil in an essential ?rst step toward ultimate utilization by plants. having a pH less than 4. P205 and K20 analysis of at least 25 weight % of Basically..g. manganese. up to 2 moles of urea per mole of 75% phosphoric acid may be employed without dilution water. it has been used in uct contains 14.0. nitrogen. This is a factor of considerable agronomic This bene?t applies not only to those trace metals signi?cance. In addition. The ?rst feature of the products of this invention that contributes to improved agronomic ef?ciency is the lowering of soil pH locally. A third element in the improvement of agronomic ef?ciency relates to the retention of nitrogen in the soil. in which nitrogen and phosphate availability are maximized. liquid fertilizer composition consists es acid on the mobility of phosphate ions in the soil. Generally. and 0 to 12 wt. and are clear liquids. if one mole of urea per mole of 75% H3PO4 is used. pref erably less than 2 and generally from about 1. similar to that from which the phosphate was urea and phosphoric acid in a mole ratio of about 0. That is. For grades of commercial signi?cance. When sulfuric acid is present in addition to phosphoric.7-37-0).1 mole up to about 2 moles of urea per mole of acid present or . preferably about 0. said product. in this process. originally freed by the action of sulfuric acid. However. This invention is particularly well adapted to the ammonia will still be lost to the atmosphere. up to about 20 weight percent in water at 0° C. the form of this invention. The liquid compositions of the present invention may be further characterized as this invention exhibit commercially acceptable stability ‘over the full range of nutrient content. The liquid fertilizers of the strongly attached as soon as it is formed. but not in (14. and (3) recovering a liquid product having a total of N. e. e. reduced. potassium chloride. One of the features of the present invention is the preparation of a complete range of ?uid fertilizers con taining combinations of the primary nutrients. (other potas sium salts such as potassium carbonate may be used Speci?cally the liquid fertilizers are the reaction prod uct of urea and phosphoric acid or a mixture of phos phoric and sulfuric acid. iron.763 4 It is a further advantage that the liquid fertilizers of used. The loss of nitrogen as ammonia to the atmosphere is a well-known phenomenon in agriculture. The amount of urea used is that required to obtain the mole ratio or analysis desired. The acid utilization of commercial grades of phosphoric acid fertilizers of this invention delay and reduce this loss by at least two mechanisms. Agricultural potash. but also SUMMARY OF THE INVENTION 55 to metal salts which may be added to the ?nished fertil without external heating. the prod sentially of: (l) admixing: 30 uble calcium phosphate. Potash may be incorporated in these also) is soluble in reasonable proportions. the present invention concerns high analy sis liquid fertilizers comprising the reaction product of urea and phosphoric acid.315. calcium ions are present in the soil in a form and to a degree that lead to the formation of insol concentrated (93%) sulfuric acid alone to form 0° C. these trace ele acid environment created by the use of the products of ments precipitate out of solution because the liquids are this invention provides sites to which ammonia is neutral or basic in nature. i. A second factor of unique importance in the enhance 25 phosphoric acid. having total N. stable liquids). The compositions of the present inven tion are clear liquids. P205 and K20 totaling at least 25 weight percent of the fertilizer in the ranges of greater than 0 to 30 wt. in the is present as an acid reaction product. as a result. stable against crystallizing at 0° C. The acids are frequently contaminated with trace metals for example. Beyond this. First. which can be a and conversion to ammonia is slowed by the fact that it useful component of the fertilizer. The gelling material is present in a viscosifying amount suf?cient to suspend ?nely divided solid parti when the usual 75% phosphoric acid (54% P205) is . ment of agronomic ef?ciency is the protective effect of The process of the present invention for preparing high analysis. natural gums and the like. the liquid compositions of the present invention do not salt out at 0° C. rendering trace elements more soluble. the hydrolysis of urea 45 and/or urea. It should be appreciated that only N and P205 may be present in some compositions and that the total analysis characterizing the composition is based on these two components.g. Acid in the formulations of this invention will achieve the same effect. would be used. This is substantially phosphate rock. phosphorus and potassium.

the urea being displaced by ammonia. usually with ammonia.924. With due attention given these factors. temperature can be allowed to rise percent.. Another and probably greater effect is the method of manufacture. means this invention. requiring up to sev eral hours in small batches to reach completion at high N values. it is found this can only be done by reducing the P level by dilu tion. the result is as shown on FIG. the solutions are viscous and the reactions slow. l.149. However. as little as lO-20% sulfuric The reaction of urea and phosphoric acid may be acid in the formula will prevent urea phosphate crystal. stable urea-phos phoric acid~K2O compositions. contrast to the prior art cited above. in fact this lization completely. prior to acid addition. Further. if any in the present compositions is less than that required to form aqueous solutions of the reaction products. however. This limitation increases the (N+P2O5+K2O) can be made as a stable liquid. The reaction of phosphoric acid and urea is exother mic... stable urea-phos phoric acid composition.' ' 5 4. in combination with low British patent speci?cation No. sulfu ric acid. i. crystallized and sepa weight is 0. conducted in dilute aqueous solutions. Prefera 4. In to prevent crystal formation. it is found that urea phosphate does not The reaction between reagent grade urea and food grade phosphoric acid. 5 to 25% P205 and 12 to 30% K20 by weight. more preferably up to about 50 weight used in the formula. FIG. An additional variable is the present invention. If sulfuric acid is be sulfuric acid. DETAILED DESCRIPTION OF THE INVENTION AND EXAMPLES is required to solublize it. with far less water than BRIEF DESCRIPTION OF THE DRAWINGS FIG. nor added directly to the phosphoric acid. or less). result of the hygroscopic nature of urea (0—5%). total nutrient content of the fertilizer compositions of The term “stable against salting out at 0° C. The system is neutralized.e. Heating is mild. FIG. i to the fertilizer composition by employing mixtures of phosphoric acid and sulfuric acid. In the process of preparing these compositions. with ranges of 5 to 15% N. further inhibits crystallization. with solutions'dilute'enough to remain dissolved (less than 25% combined N+P2O5 calculated on a K20 free cles.6:1. the phosphoric acid should rated from the reaction mixture. is a factor in that substantially no precipitation of materials occurs in their stability. This is believed to be due in part to the presence of other com material. suspend ?ne insoluble particles. in which urea is reacted as a solution in water. a problem to which no prior art has been ducted at the lowest temperature consistent with ac to about 80 weight percent of the total acid content may 0 ceptable reaction rate (100° F.It is unexpectedly found that. In all the prior art relating to urea-phosphoric acid combinations. use temperature reaction. Thus. and. they do not do so. 1.763 6 . To prevent the crystallization of urea phosphate from concentrated acid solutions. e.e. by simply stirring the mixture of urea and acid. 1 is a binary graph of 0° C. The water present. the presence of water in the compositions high in K20) sulfuric acid is again useful fertilizer compositions reduces the nutrient content. suspen sions containing 50% of combined nutrients can readily be made. the urea may be (which cannot contain urea phosphate at any rate). a viscosifying agent which will increase the viscosity of liquid in question to a degree suf?cient to achieve the desired result. If water is used as the diluent. Among these in?uences. i. 50 to 1000 microns. so that urea phosphate does not exist.. stable urea-sulfuric acid-phosphoric acid compositions. 75% can be conducted to give products of analysis up to 22-28-0 (N-P-K). this limitation of water is in stark the liquid fertilizers at 0° C. some water will normally be the source of the phosphoric acid. furnace grade acid present in phosphoric ‘acid (lo-15% usually). as will be seen below. which serves to neutralize the phosphoric acid. 3 is a graph showing 0° C. the urea has been dampened or slurried with water so that it remains dissolved. This weight ratio . Limiting the water content of the method has been used in the prior art. some as a forms crystals more readily than wet process acids. water is not the solvent for the present liquid composi tions. one or more of these conditions prevails: maintaining good low temperature stability. as is shown later).). where the weight ratio We are not here concerned with neutralized solutions of nitrogen to P205 is less than 0. When this is done. 2. in which the reaction between urea and phosphoric acid is conducted at mod erate temperatures. substantially (up to 180° F. Theobject of this invention is to make urea phos phate in a concentrated acid system and to keep it in stable solution. _ ~ ponents in the complete formulation.6:1 or greater. preferably from 5 up addressed. as a contaminant or processing aid. Urea is decomposed to form ammonia. crystallize from these compositions even though-they far exceed the normal solubility of the urea phosphate.. some some water (up to 40% of the weight of urea) may be free sulfuric acid. g. where it can be seen that actual N concentra 60 tion falls as the system is diluted. or other contaminants (these acids added as a processing aid to slurry the urea and expedite the contact of urea and the acid. while many of the com positions of this invention contain urea phosphate in concentrations that should crystallize at low tempera ture according to prior art. although water may be present as described above. the reaction should be con The “viscosifying amount” means that amount of a . However. i. Urea phosphate is formed.e.315. advantageously be added directly to the urea. if a of water solutions is detrimental to the salt out stability particular formula calls for additional water (as with of the system and of course. 1. 2 is a ternary graph of 0° C. potassium chloride and contaminants occurringv in wet process phosphoric acid have been found in this work to reduce the tendency of urea phosphate crystals to form and grow. any acid formation within present during the reaction between urea and phos the limits given below. If it is desired to increase the ratio of N to P. it proceeds at a rather slow rate. and probably because the latter contain less water. it has been found that where the ratio of nitrogen to P205 by 3. above 25% combined nutrient phoric acid is thus limited. This reaction rate can be increased and sulfur can be added basis). for example. This is ac complished without added water. Urea phosphate is formed in dilute enough solution 65 bly. Finally urea enters the system as a 45 solid or at most a heavy slurry. the amount of water 25 differ among themselves. as noted above in system as explained above.

has about the same phosphate content as the remainder of the acid. when potassium (in the form.5 tions. so no effect on the assay is noticeable due to the modest amount of insoluble material which might settle out. No. 2'(line U-SA .01 0. and some organic residues or carbon. Al)3 KH14 (P04)3. > Turning now to the use of ?eld grade materials in the .03 0.8 0. 9. the urea can be slowly added to the acid with V Na K‘ F S03 SiOz C Solids‘ stirring. phosphoric acid and urea free sulfuric acid.2 52. line “U-SA PA” shows the results that can be achieved by this method.' bining urea. % Constituent A B C D E mally result.9 1. Pat. 3. special procedures are needed to make the concentrated product on a commercial basis.3 0.04 0.. Consequently. Wt. sulfuric acid and phosphoric acid directly. FIG.04 0.04 0. although with urea in good condition and certain acids (including furnace grades) the compounds described can be made. some difference in be havior must be expected when making compounds de scribed above using ?eld acids. (Note US.3 0.7 3. 2 with a wide-.variety of ?eld acids. These solutions are completely miscible in all propor P205 Ca Fe 54.2 0. it is possible to prepare the analysis of some ?eld grade materials. with stirring. Using this method.04 0.3 0.763 8 corresponds to a mole ratio of urea to phosphoric acid presence of metal salts and sulfuric acid.4 0.8 8. No heating is observed in mixing.6 Mg Cr 0. with speci?c gravities ranging from about 1. present in the acid. black). dried 1 hour @ZZOF Source: Encyclopedia of Chemical Technology. some heat generation accompanies this opera tion. gener In any ?eld situation.8 52. again depending with pre-reacted urea-sulfuric acid. adding any water required for the formulation.713.1 0. Because of the high intensity of the urea-sulfuric acid reaction. 40 To do this. In storage. Slow addition of the remain der of the acid while stirring brings the system to com relevant to their performance in making the fertilizer compounds described is the slow precipitation of a complex iron-aluminum-potassium phosphate. 2nd Ed. it can be used as a base for further manufacture. TABLE I Composition of Commercial Phosphoric Acids. of potassium chloride solution) is added to such an. adding urea in sufficient quantity to double the size of the ?nished batch.9 0.1 0. ?eld acids are highly colored (green.4 2.7 53.01 1. further precipitation of the complex salt occurs. 1.3 0.1 .2 2. it must be presumed that some carbamate is present in the urea. 2 (line U-SA salts. With such to 1.01 0.95 and viscosities are high as 1000 op. that is. it is desirable to add the acid slowly to the urea while tumbling. In such cases. carbon dioxide is given off and solid ammonium phosphate is formed.7 of 1.1 0. combined and mixed. and slowly adding the sulfuric acid while stirring. While Food compositions shown in FIG.1 0. the two acids are measured. in fact. If however.1 1. ' 4.7 0. In these cases. ' N-P solutions with sulfur can be made by blending urea-sulfuric acid (USA) with phosphoric acid'(PA).05 0.5 the line marked '“USA-PA” gives the compositions available by this technique. de composition may result if this procedure is followed.7 = 0.04 5. here the heat ‘ release is appreciable. Leaving a heel of liquid in the vessel permits further manufacture to be conducted in a stirred ?uid mass.2 0.9 0. p.01 0. and of good stability if kept covered to exclude atmospheric moisture pick-up. notably some of these occurring in ?eld this method it is possible to combine more urea and phosphoric acid in the product with a given amount of 50 grade phosphoric acids. with a speci?c gravity of 1. If the 5 desired product requires acid of 50% concentration or 20 less. the acid is stronger than this. certain limitations arise due to the condition of the urea and/or the compo It is consequently found that with ?eld grade materi als his not generally possible to reproduce FIG.802. A1 0.01 0. cols. some carbamate is probably present in most urea as it is supplied. after a fraction of the acid 25 ‘Filtered. acid with modest amounts of iron and/or aluminum still by placing theliquid in a stirred vessel of appropriate size.4 0.8 0.2 0. (Fe.315.1 0. ammonia and carbon dioxide. particularly under warm wet conditions to sulfuric acid in the mix (higher sulfuric acid content 45 produce ammonium carbonate. Table I gives PA).3 1. with corre spondingly reduced water content.02 0. This compound forms continuously until the component in shortest supply is virtually depleted. a stirrable slurry is formed. brown or 65 achieved when the urea is in good condition. further hydrolysis of the urea may occur.6:1 or greater avoids crystallization or salting out that would nor these compositional variations.8 0. but since both liquids are viscous.574 and a viscosity less than 100 cp Highest assays and best stability in storage are at 70°F.03 0. depending on concentration) has been'added.1 0. Reaction is rather rapid. as a result ?eld grade urea is likely to be appre ciably different from reagent grade product. The urea is then added. Best results with ?eld materials have come with the use of sulfuric acid.2 0. preparation of these compounds. however.04 0. The high urea and a variety of ?eld grade acids. The salt.5 0. 4 and 5).07 0.2 0. 88 Another feature of these ?eld grade acids that will be (20-30%.2 0. ' Grade acid of the same strength is water-white.5. 1. In FIG. .1 0.2 0. 2.01 0. 2. By metal salts. ' This type of degradation is accelerated by high temper ature and low pH.3 0. N-P solutions with sulfur can also be made by com.4 0.0 0.6 0. .7 53. i The degradation of urea can be catalyzed by certain somewhat on the proportion of sulfuric acid present. This is done tassium. this is usually po plete reaction.03 0.1 0. a broadrange of sition of the phosphoric acid. As a consequence of The procedure of adding the phosphoric acid'to the urea when the weight ratio of N:P2O5 is 0.5 2. say. depending on the proportion of generating more heat). some agita tion is required to produce a uniform blend. 4H2O.8 0. sulfuric acid than can be done by blending phosphoric ally being complete in 15-20 minutes. Vol. Field grade phosphoric acid generally contains some values of viscosity and speci?c gravity indicate the N-P-S compositions represented by FIG.01 0.03 0. Once a batch of liquid product has been made.65 when it has undergone little or no hydrolysis. some dissolved or suspended metal 60 as described above and shown in FIG.

within the envelope curve. but main PA . 371 grams of wet process phosphoric acid. such as 10-37-0. If it is desired to increase the potash level beyond the limit of solubility. In most cases. Analysis of the product was 17-34-0. with the same N-P ratio. This material was Sulfuric acid (66 Be) and wet process phosphoric acid (0-54-0) were mixed in the proportions 80 to 745 grams. Generally. if two liquids of 0° C. when laboratory materials are used.' tioned above.315. select the ratio of N to P. While stirring. 1 2 3 4 5 6 7 8 9 10 U . so can into a slurry. The numbers (weight percent) represent the compo show the slightly anomalous behavior referred to nents (N-P2O5-K2O-S).4. % Wt. Mild heat evolution occurred. with pH of 1. occasionally an acid is encountered which does not permit making the higher analysis com EXAMPLE 2 435 grams of urea was wetted with 194 grams of pounds on or near the envelope curve. Blend in solid potash to reach any point along the tie line. stirring. S G 5 ‘points to the left of line E require water. warrn. however. 175 grams of urea was added. stable at 0° C. “ points to the left of line E require water.Urea 17. One method of producing these materials is to prepare a KCl solution and blend it with the N-P liquid of choice. and such acids can be used for lower grades.786 0. With fur nace grade acids this type of reaction does not occur.7 4. but would slowly dissolve in the soil solu 55 EXAMPLE 3 tion. mixture. The mixture was stirred. that for the most part the liquids blend arithmetically. The liquid fertilizers are analyzed and the analysis reported. 54% arises with ?eld grade acids is the potash reaction men P205. somewhat more K can be introduced. the solution can be blended with KCl solution. % Blend U PA SA N P K . that is. however.5 2. they should not be viewed as re shown in FIG. because it does not reach serious proportions immedi miscible in all proportions with phosphoric acid to give ately andthere would normally be time to apply such a lower nitrogen-phosphate ratios. This behavior is this invention make excellent suspensions of very high total analysis. and the thickeners of viscosifying agents conventionally used in suspension fertilizer technology with neutral compositions are all effective with these acid materials.5 22 26 30 35 39 43. 3 the N-P on FIG. 1 35 EXAMPLE 1 along the abscissa. The N/P2O5 5 3 2 l 0. viscous liquid. where any composition within the envelope curve can be made. the ends of this curve stricting the scope of the claims to which the inventor is otherwise entitled. further.5 48 53 57 74. This effect plete in 15 minutes.7 7. 1. locate along the abscissa the total N-P content permissi ble where: Point A B C D E‘ F respectively. The product was ?uid.5 product was a clear. the composition of the base N-P solution (urea. clear and may not rule out the use of a given acid. 3 the N-P blends contain water and follow the To 630 grams of 75% furnace phosphoric acid (Food Grade) 370 grams of urea was added with moderate stirring. These are prepared from the acid fertilizer base containing the The N-P liquids described above and illustrated in FIG. The acid fertilizer liquids of full N-P-K liquids. It is found.0 From this value and the ratio. Solu . stable to A number of these compositions can be made with storage at 0° C. To use FIG. 3 represents the compositions shown in FIG. below 50% N+P on FIG. 1.5-0. the blend will have the same stability. 3.6 5.phosphoric acid SA . the sediment is relatively insoluble in 5-45. phosphoric acid and water if indicated) can be found. it analyzed 8-40-0-2. The following examples illustrate that claimed as the invention. 2 can be augurnented with K to make 20 other desired nutrients according to procedures well known to those in the art. 2. desired. 40 of the urea was complete in 15 minutes.2 TABLE II N-P solutions with S made with ?eld components Wt. 3. In some regions of composition. generally following the envelope up and to the left. It analyzed 20-20-0. and solution was com. Mild warming occurred. so its nutrient value would not be lost.1 3. with brief mild stirring the urea disintegrated the N-P solution can be made with a ?eld acid. To the stirred mixture 570 grams of urea was added.5 69 64 59 53 48 41. suspensions must be made. 65 EXAMPLE 4 260 grams of sulfuric acid (66 Be) was mixed with 170 grams of wet process phosphoric acid.5 23 26 8 10 12 14 16 18 20 22 24 26 40 37 34 31 28 26 22 18 13 9 0 0 0 0 0 0 0 0 0 0 2. stabil ity are blended in any proportion. etc.7. The product was a ?uid water-white material of pH 1. this ' ' 15 procedure dilutes the total nutrient content.5. FIG. above.sulfuric acid tains the N-P ratio. If a higher potash content is needed. if 45 water. the solution. Solution was complete within ten minutes.4 3. 54% P205. exhibiting mild 60 warming. One problem that . with three or four numbers.5 33. which causes sedimentation. To this slurry was added. with moderate the appropriate N-P-K solution.0 4.763 PA) are readily made as shown in Table II which is extracted from FIG. ?eld grade acids.5 24 17 8 9 l0 11 12 13 15 18.1 8.8 3. Compositions between 54 and 50% combined N and P are those shown in the right-hand portion of FIG.5S. and the solution - compositions shown in the left-hand portion of FIG. 1 and FIG. stable. Point 10 -continued N/P205 0.

55 EXAMPLE 9 A mixture was made of 445 grams of the product of Example 5 with 555 grams of the product of Example 8. the product of Example 8. Fertilizer C: Acid 24-l2-O-4S. was added. pro cessed under conditions which produce large amounts of polyphosphoric acid which is reputed to have good compatibility with metals. At this point 410 grams of potash was blended in. The heat of dilution of the acid aided the solution of the potash.7 collected and monitored.11 clear.5. after a few minutes of agitation 267 grams of wet pro cess phosphoric acid was added. 54% P205. The results of these experi could be made with equal ease.8-5. 10 2. ranging in character from sandy through ?ne with good stirring. stable ?uid analyzing 26-9-O-8S. Fertilizer B: Ortho 10-34-0. down to —7‘‘ C.5 C Clay Loam 4. neutral. at room temperatures of 24°-27° C. Duplicate samples of each soil were also The product of Example 5 was mixed with additional treated with the reaction product of urea and sulfuric wet process phosphoric acid in the ratio of 591 grams to 409 grams. and within a few minutes it was in solution. 25 ments are tabulated below. EXAMPLE 13 continued until all the acid was incorporated into the mass. The resulting solution was fluid and Soil A B Nitrogen Loss From Surface. EXAMPLE 8 653 grams of urea was placed in a beaker and moist D Fine Sandy Loam 5. however. EXAMPLE 10 60 sition as above but cold processed so that no poly ‘acid is formed. The Fertilizer A: Conventional 10-34-0. EXAMPLE 5 4. water-white liquid analyzing 30-0-O-lOS. In each case.763 analyzed 9-10-30-3S. this is why the more expen sive processing is done.7-4.8-39-1. with a pH of 1. a high nitrogen acid grade according to the present invention.6-6.1 Treatment Urea/water Urea/acid Urea/water Urea/acid Urea/water Urea/acid Urea/water Urea/acid 72 hrs.7-18.9-27.5 163 4 30 0 121 1 168 hrs. sulfuric acid.85 5. It stored well at low temperatures. The solution becomes very cold and the potash normally dissolves very slowly. The product was a viscous. 9.2-36.potash started to appear after two 15 weeks. then stopped while the material cooled and entrained air escaped. within ?ve minutes. The improved compatibility of trace metal salts with the acid fertilizers of this invention was demonstrated by adding zinc sulfate (36% zinc) to several complete fertilizers. The resulting suspension 407 grams of urea and 65 grams of potash (potassium chloride) were wetted with 182 grams of water to disin tegrate the urea and form a heavy slurry. and the speed of agitation was increased to a mild level.95 stable. With very mild stirring the mixture was 20 acid. To this was added 308 grams of urea 65 metals. fluid and free of undissolved material. Slow addition of acid was the atmosphere is greatly delayed and reduced in soils of agricultural signi?cance by acid compositions such as those according to this invention. analyzing 7. The fluid suspension thus prepared analyzed 9-l5-25-3S. the same compo resulting fluid fertilizer analyzed 25-8.8-2 and 7. and 346 grams of wet process phosphoric acid. The decompositions of urea and loss of ammonia to slowly with slow agitation until approximately 15% of the addition was completed. After stirring for 15 minutes the solu tion was clear. EXAMPLE 6 sandy loam to clay loam. and mixing continued for an additional 10 minutes. EXAMPLE 12 To illustrate the effect of low pH fertilizers on soil.. 12 tion was effected rapidly. To this mass was added 327 grams of commercial 66 Be sulfuric acid in the following manner: Acid was added Note that from urea/water the nitrogen losses in one week are a very large part of the material added. Mg. Type Clay Loam Sand pH 6. Simple stirring of the two viscous liquid for a few min utes was suf?cient to effect complete solution. The soil sam completed in a few minutes to give a clear. Potash in the amount of 492 grams was .2-2l. Into this mixture was incorporated 6 grams of Xanthan gum with stirred slowly for a few minutes to complete the action.3-1. and stirring was contin ued for ten minutes. 65 grams of wet process phosphoric acid was incorporated. To 249 grams of water was added 97 grams of potash four soils. giving a then blended into the mixture. Stirring was continued for a few minutes. 387 grams of the product of Example '5 was then added. The importance of this property of the products of this invention is very substantial. the product of Example 8.2 ened with 20 grams of water while slowly stirring. the level of nitrogen added to the soil was 280 mg. Analysis of this product was 18. some crystals of . on dilution with water no heat was evolved. This was EXAMPLE 11 A mixture of 306 grams of the product of Example 8 and 278 grams of wet process phosphoric acid was made by thorough mixing for a few minutes. for extended periods. following this addition. It was found that other face to the atmosphere as ammonia was continuously ratios. such as 13.8-3. ?uid stable ples were so arranged that nitrogen lost from the sur product analyzing 11-33-24. neutral. thorough mixing for 10 minutes. At this point the mass had 45 liqui?ed into a mixable slurry.5S. until gellation began to occur. giving loss measurements EXAMPLE 7 made at 72 and 168 hours. were treated with a solution of urea in water. that in a neu A suspension fertilizer was made by pre-gelling 15 grams of attapulgite with 120 grams of wet process tral product would present great dif?culty with trace To each of the above was added 2% by weight % zinc sulfate with good stirring to assume uniform mix tng: phosphoric acid. 93 10 275 4 81 7 200 2.315.

Similar results are obtained with manganese sul fate. urea to acid can successfully be covered with wet pro . (external heat) Crystals in 1 day 2.6-44-0 No crystals (1 yr. urea added to 68. 2 or 3 wherein the total N. on the other hand. (external heat) 200° F. +) No crystals (1 yr. Within a few minutes ?ne crystals of urea phosphate The superiority of the acid formula in the mix tank is apparent. 1. which does not salt out at 0° C. No crystallization oc curred. non-ammoniated. 1 hr. A high analysis. 6. (external heat) 140" F.57. below. These two grades represent ex was treated with 15% by weight of sulfuric acid. equal weight of 20% potassium chloride solution. This effect carries along after application as well. ?uid) and a wet process grade (green sp gr IV. with such acids as standing materials (see Example 16). They also indicate that an area of potential wherein the trace metals include one or more of the concern with very clean acid exists in the low urea metals zinc.5 g. not in solution would be uniformly applied venting crystallization are illustrated. Sample C from Example 15. The fertilizer composition according to claim 55 wherein potassium chloride is present. they demonstrate that it is possible to overcome the natural tendency of these concentrated solutions to crystallize. % P205 and 0 to 12 wt. Sample A from Example 14 was mixed with an without equipment problems. stirred to completion Each acid was reacted with urea in a mole ratio of 1:1 1. II. (external heat) No crystals (1 yr. Wet Process Z l % 2 1 % 22-28-0 14. 12. as a ?nely divided solid. EXAMPLE 16 B All the material precipitated and settled to the bottom. The high analysis. stirred No crystals (1 yr. liquid fertilizer according to 4. tals already present and prevented them from forming again.315. 35 and characterized as a clear liquid.7-37-0 8. The fertilizer composition according to claim 1 These results show that the useful range of ratio of 65 containing trace metals. the deleterious effect of excessive water and the bene?cial effect of sulfuric acid in pre C A light uniform haze developed which did not settle. tered in practice. P205 and K20 analysis is at least 30 weight % of the fertilizer. between them in compositions. Wet Process E. Furnace C. very viscous). ' 5. 5 to 50 wt. % N. another common source of a trace metal. and that additional steps may be necessary to prevent crystallization in this region A An estimated 50% of the added material settled out as sticky lumps that would plug screens. 8. manganese. The fertilizer composition according to claim wherein a viscosifying amount of gelling material 1 7 1 is additionally present for suspending finely divided solid particles. (autothermal) 125° F. upon which prior art is based. _ EXAMPLE 14 This example shows the advantage of low tempera III. were each treated with sulfuric acid. Furnace B. 9. The high analysis. (1 yr. liquid fertilizer according to claims 1. and observed. (10 minutes) under the temperature conditions given 30 inhibits crystal formation.5 to 4. +) No crystals (1 yr. has a pH of less than 4 and has an analysis of N and P205 and K20 totaling at least 25 weight percent of the fertilizer in the ranges of >0 to 30 wt. 15% sulfuric acid by weight dissolved the crys centrated solutions. The high analysis liquid fertilizer according to claim 1 having a pH in the range of 1. The fertilizer composition according to claim 11 cess acid. 10. stir 60 No crystal. Sample D from Example 14 was mixed with potas sium chloride solution as above. Samples B and C from Example 14. The fertilizer composition according to claim 9 wherein potassium chloride is present in excess of its solubility in said composition. sp gr 1. Wet Process F. Sulfuric acid (6% by weight) added to the solution dissolved the crystals and prevented their 15 reappearance. Crys tremes. both 54% P2O5:furnace grade (water white. the small fraction of the zinc. The fertilizer composition according to claim where a potassium-containing component is present.6-44-0 22-25-0 14. +) wherein said pH is less than 2. Wet Process F. Furnace C. Furnace D. Furnace D. water encourages the crystallization of urea phosphate. Finally. 11. % K20. Wet Process ‘ 75° F.95. These results show that in the absence of other stabi lizing in?uences. (autothermal) 175“ F. The invention claimed is: (31. Furnace B.7-37-0 8.5 g acid). after crystallization. Two different phosphoric acids were used. stirred Crystals in 20 min. In both venting the crystallization of urea phosphate from con 20 cases. claim 1 wherein the reaction product is that of urea and illustrate the range of conditions likely to be encoun 45 a mixture of phosphoric acid and sulfuric acid. 1. +) No crystals (1 yr.13 Fertilizer Observation 4. Wet Process 200° F. They also phosphoric acid. after crystal ture processing under autothermal conditions in pre lization. . 7. and all acids encountered in the ?eld would be 25 tals were dissolved and did not reform. liquid fertilizer according to claim 1 wherein the reaction product is that of urea and These results clearly show the advantage of autother mal processing in preventing crystallization. The high analysis. +) Fine crystals.763 14 portion of the spectrum. began to form. aluminum or iron. +) Crystals in 1 hr.. +) Crystals in 2 days which is the reaction product of urea and phosphoric acid or a mixture of phosphoric acid and sulfuric acid. In this example. The fertilizer composition according to claim 5 EXAMPLE 15 The two phosphoric acids used in Example 14 were reacted autothermally with urea in different mole ratios: Mole Urea Acid Ratio Acid Composition Observation A. 3. 40 E. Sulfuric acid. liquid fertilizer Acid Temperature Observation A.

adding urea thereto.15 essentially of: 4. phosporus and sulfur comprising admixing said phosphoric acid with 5 to 80% of its weight of nitrogen and phosphorus in a weight ratio of N:P2O5 of 0. The fertilizer according to claim 24 wherein said urea is dampened or slurried with water prior to acid 17. 20. and (3) recovering a liquid product having a total of N. 26 or 27 wherein at least 1 mole of urea per mole of acid is pres 35 ent. non-ammoniated.about 2 moles of 45 . % P205 and 0 to 12 wt. The process according to-claims 13 or 16 wherein said urea is dampened or slurried with water prior to acid addition. 14. and (3) recovering a liquid product having a total of N. phosphorus and sulfur comprising admixing saidv phosphoric acid with 5 to 80% of its weight of sulfuric acid. A process for preparing high analysis. . allowing said phosphoric acid and urea to react.of urea per mole of acid is present. and allowing said acids and urea to react. liquid fertilizer composition consisting percent of the fertilizer in the ranges of >0 to 30 wt. P205 and K20 analysis of at least 25 weight % of to urea. and allowing said acids and ‘urea to react. I i ‘ trogen and phosphorus in a weight ratio of N:P2O5 of 15. 16.315. The fertilizer according to claim 24 containing nitrogen. liquid fertilizer composition containing lize said urea is added thereto. The process according to claim 13 for preparing a high analysis. non ammoniated.1 to about 54. P205 and K2O_ analysis of at least 25 weight % of I said product. ~ 31. The process according to claim 20 wherein at least 1 mole of urea per mole of acid is present. 5 to 50 wt. The process according to claim 13 for preparing'a 29. 21. adding urea thereto. liquid which does not salt out at 0° C. The process-according to claim 13 wherein said phosphoric acid is wet process ?eld grade phosphoric acid having a P205 analysis of about 52. 22. high analysis.1 mole up to about 3 moles to urea per mole of acid present I phosphoric acid in a mole ratio of about 0.. mole . The process according to claim 13 wherein potas¥ 20 25. The high analysis. said product.1 mole up to about 3 moles of urea per mole of acid present (2) reacting said urea and said acid exothermally and without external heating in the presence of less water'than required to form aqueous solutions of the reaction products.' urea anda mixture of phosphoric acid and from 5 to 80 weight percent sulfuric acid based on said phosphoric acid in a mole ratio of about 0. The process according to claims 13 and 14 0. which is nor mally soluble in said liquid product is added thereto in 55 excess of the solubility of said potassium compound. the reaction products. - (l) admixing: 2 urea and wet process phosphoric acid in a mole ratio of at least about 1 mole up to . allowing said phosphoric high analysis.6 to 22 wt. non ammoniated. mixing said materials.1 mole up to about 3 moles to urea per mole of acid present (2) reacting said urea and said acid exothermally and without external heating in the presence of less water than required to form aqueous solutions of 23. has a pH of less than 4 and has an analysis P205 and K20 analysis of at least 25 weight % of said product. liquid fertilizercomposition containing nitrogen. % and P205 is 25 to 44 wt. A fertilizer according to claim 24 containing ni sium is added as soluble salt. h . % K20. 30. The process according to claim 13 wherein a viscosifying agent is added to said liquid product'and a solid particulate potassium compound. A process for preparing high analysis. The process according to claim 13 for preparing a addition.5 mole up to about 2 (1) admixing: urea and wet process ?eld grade phosphoric acid in a mole ratio of about 0. liquid fertilizer composition containing nitrogen and phosphorus comprising admixing urea and said phosphoric acid. 19. and characterized as a clear. urea per mole of acid present or. mixing said materials. 18. A high analysis. The process according to claim 13 for preparing a 25 26.6 or morezl consisting of adding said phosphoric acid to urea.urea and a mixture of phosphoric acid and from 5 to 80 weight percent sulfuric acid based on said phosphoric acid in a mole ratio of about 0.. prepared by the process consisting essentially of: (l) admixing: urea and wet process ?eld grade phosphoric acid in a mole ratio of about 0. The fertilizer according to claim 24. liquid fertilizer according to claim 1 wherein N is 8.763 16 13.5 mole up to about 2 moles of urea per mole of acid present or urea and a mixture of phosphoric acid and from 5 to 80 weight percent sulfuric acid based on said moles of urea per mole of acid present or . ' sulfuric acid.6 or morezl consisting of adding said phosphoric acid wherein additional urea and suf?cient water to solubi (2) reacting said urea and said acid exothermally and without external heating in the presence of less water than required to formaqueous solutions of the reaction‘ products. liquid fertilizer composition wherein said phosphoric acid is’ wet process furnace grade phos phoric acid.8 wt. % N. 24. %. mixing said materials. 28. 25. acid and urea to react. %. . " .liquid fertilizer which is the reaction product of urea and phosphoric acid or a mixture of phosphoric acid and sulfuric acid. liquid fertilizer composition consisting essentially of: high analysis. The process according to claim 18 wherein at least.l. and (3) recovering a liquid product having a total of N. * * * * * of N and P205 and K20 totaling at least 25 weight 65 . mixing said materials. 30 27.