Патент USA US3028230код для вставки
April 3, 1962 E. H. BROWN 3,028,217 TRICALCIUM DIAMMONIUM PYROPHOSPHATE Filed June 3, 1959 CALClUM vn'nuous METAPHOSPHATB i ""I‘.“ EXTRACTION AND PHASE SEPARATION SUPLRNATANT AQUEOUS PHAS a VISCOQS PHASE CRYSTALl-IZATION OF C53 Hz (P2O7)z. 444,0 CRYSTA Ll-INE MA 58 r- WATER WASHING CRYS TALS WASHINGS AMMONIUM HYDROXIDE ‘— CRYSTALLIZATION OF TRI'CALCIUM DIAMMONIUM PYROPHOSPHATU MO'I’HIZR LIQUOR CRYSTALLINE PRoDuc'r \ (fan/(3m INVENTOR. BY?’ United States Patent 0 1 3,028,217 ar 1C€ Patented Apr. 3, 1962 2. 3,028,217 dation products of calcium metaphosphate. The super natant aqueous phase is formed in much greater volume Valley Authority, a corporation of the United States Filed June 3, 1959, Ser. No. 817,956 little phosphate. This supernatant solution must be drawn otf continuously as it is formed it any reasonable degree of purity of the viscous-phase material is to be attained, TRICALCIUM DIAMMONIUM PYROPHOSPHATE Earl H. Brown, She?ield, Ala., assignor to Tennessee 2 Claims. (Cl. 23-107) (Granted under Title 35, US. Code (1952), sec. 266) than the heavy viscous phase, but it contains relatively because the aqueous solution may become su?iciently concentrated in shorter chain calcium metaphosphate polymers to cause the materials in the two phases to be The invention herein described may be manufactured and used by or for the Government for governmental pur 10 come partially miscible in each other. When the supernatant solution is continuously drawn poses without payment to me of any royalty thereon. off, the viscous phase is a sirupy mixture of hydrated poly_ This invention is a new pyrophosphate and a process mers of calcium metaphosphate containing from 30 to for its production. 60 percent of Ca(PO3)2, polymerized in relatively long Principal objects of the invention are to provide a new material suitable for fertilizer and other uses and 15 chain molecules. When extraction is complete, the heavy viscous phase is to provide a process for its manufacture. separated from any residual supernatant solution. The The new material is tricalcium diammonium pyro separated viscous phase is then held in a closed vesselv phosphate. It may be produced by digesting crystalline until crystallization occurs. On standing, this material tricalcium dihydrogen pyrophosphate in an excess of am monia. A process for the’production of tricalcium di 20 ?rst becomes a gel and then a mass of crystals. The resulting crystalline material is tricalcium dihy hydrogen pyrophosphate is shown and described in my copending application Serial No. 817,952, ?led June 3, 1959, now abandoned. drogen pyrophosphate, Ca3H2(P,O7)z-4H2O, mixed with some orthophosphate. The crystals are washed with water, which removes orthophosphate. Tricalcium di I prefer to produce tricalcium diammonium pyrophos phate from vitreous calcium metaphosphate by a process 25 hydrogen pyrophosphate is then treated with an excess of ammonium hydroxide in high concentration. Reaction which comprises soaking with water in a reaction vessel between the tricalcium dihydrogen pyrophosphate crystals ?nely divided vitreous calcium metaphosphate to promote hydrolysis thereof, producing an extract consisting of two phases, namely, (1) a heavy substantially water-insoluble and concentrated ammonia goes well at room tempera~ ture. A crystalline product, tricalcium diammonium py viscous phase and (2) a supernatant aqueous solution of 30 rophosphate, Ca3(NH,)2(P2Oq)2-6H2O, is formed. When fertilizer-grade vitreous calcium metaphosphate water-soluble degradation products of vitreous calcium is used as starting material, there is no separation of metaphosphate; continuously separating the phases; con phases in the aqueous extract produced. Apparently tinuously withdrawing the supernatant solution during ex silica present in the fertilizer-grade material causes the traction; separating the viscous phase from residual super natant solution; holding the separated viscous phase until 35 degradation reaction to proceed faster than the phases will separate under the in?uence of gravity. The entire it becomes crystalline; washing orthophosphate from the extract is a single viscous phase. It is treated exactly as resulting crystalline material; and digesting the resulting described above for the viscous phase obtained from pure crystalline tricalcium dihydrogen pyrophosphate with an calcium metaphosphate. The end result is the same ex excess, preferably about 6 times the theoretical quantity, of concentrated ammonium hydroxide. The crystalline 40 cept that the product contains impurities derived from the impure startm'g material. ' product of the digestion is tricalcium diammonium pyro~ phosphate, which normally crystallizes with 2 molecules Example of water present. Vitreous pure calcium metaphosphate was crushed and The attached drawing is a ?owsheet illustrating dia screened to separate a fraction of size to pass a standard grammatically a method for the preparation of this new 45 20-mesh screen and be retained upon a 60-mesh screen. material from calcium metaphosphate. About 50 grams of the sized calcium metaphosphate was The preferred starting material is ordinary vitreous cal introduced into an extraction vessel. Distilled water was cium metaphosphate. Either chemically pure or fertiliz added to the extraction vessel dropwise while the vessel er-grade material is satisfactory. This calcium meta and contents were maintained at a temperature of about phosphate is ground to a degree of ?neness which will 50 50° C. An extract consisting of two phases was formed. depend upon the method of extraction used. For exam These phases were: (1) a dilute aqueous solution of ple, simple percolation of water through a bed of crushed short-chain degradation products of calcium metaphos calcium metaphosphate at room temperature is one satis phate, and (2) a heavy viscous phase which was substan factory method for carrying out extraction. immiscible with water or with the dilute aqueous When this method is used, the calcium metaphosphate 65 tially solution. The phases were separated as formed by dif preferably is in particles from —20 to +60 mesh in size. ference in speci?c gravity. The supernatant aqueous Inclusion of much material ?ne enough to pass a ‘60 phase was continuously drawn off during extraction. mesh screen will cause a bed of calcium metaphosphate The viscous phase was then separated from residual particles to mat together, and the resulting mass does not supernatant aqueous solution and was placed in a closed have enough voids to permit free passage of liquid. 60 vessel and there held until it became a crystalline mass, Preferably, the extraction may be carried out with consisting essentially of tricalcium dihydrogen pyrophos use of a stirring device arranged to keep the particles of phate in admixture with a small proportion of orthophos calcium metaphosphate in motion in extraction water. phate. The mass was then washed with su?cient water When exn'action is conducted in this manner the calcium metaphosphate may be of smaller particle size, since the 65 to remove orthophosphate. The resulting crystals of tricalcium dihydrogen pyro material dies not adhere while in motion in water, and phosphate were then treated with an excess (about 6 the advantage of greater surface contact with extraction water per pound of calcium metaphosphate is gained. times the theoretical quantity) of concentrated ammonium hydroxide at about 20° to 35" C. The resulting mixture I have found that the extract consists of two phases when pure calcium metaphosphate is used as starting ma 70 was held in a closed vessel until reaction was complete. The process just described was repeated twice. In each terial: (1) a heavy viscous phase immiscible with water, and (2) a supernatant dilute aqueous solution of degra case the crystalline product produced was tricalcium di 3,028,217 4 ammonium pyrophosphate having the compositions shown soluble degradation product of vitreous calcium meta by the following table. ' phosphate; continuously separating said phases; continu ously withdrawing the supernatant solution from said re Composition, percent Mole ratio action vessel; separating said viscous phase from the re~ P105 sidual supernatant solution; holding said separated vis cous phase until it becomes crystalline; washing ortho Run CEO 1 ________ -. 2 ........ _3 ........ -- 27.42 27.59 27.26 Pros 46.34 46. 61 46.38 NH: 5.5 5.3 5.5 H_:O CaO (di?'.) 20.74 20.50 20.86 1.50 1.50 1.49 NHs H2O phosphate from the resulting crystalline material; digest ing the resulting crystalline tricalcium dihydrogen pyro 1.0 1.0 1.0 0.99 0.95 0.99 3.53v 3.48 3.54 phosphate with an excess, of the theoretical quantity, of 10 concentrated ammonium hydroxide; and withdrawing the crystalline product ‘from said digestion step as tricalcium These products had the same characteristic optical prop crties and X-ray diffraction pattern. I claim as my invention: diammonium pyrophosphate having the formula . 1. A process for the production of tricalcium diam 15 monium pyrophosphate which comprises the steps of soak ing with water in a reaction vessel ?nely divided vitre ous calcium metaphosphate to promote hydrolysis there of whereby a mixture of hydrated polymers of rela 2. The process of claim 1 wherein the step of digest ing the crystalline tricalcium- dihydrogen pyrophosphate with an excess of concentrated ammonium hydroxide is carried out at a temperature of about 20° to 35° C. tively long-chain molecules of calcium metaphosphate 20 containing from about 30 to about 60 percent of Ca( PO3)2 is formed, producing an extract from said water-soaked calcium metaphosphate consisting of two phases, name 1y, (1) a heavy, substantially water-insoluble viscous phase and (2) a supernatant aqueous solution of water 25 References Cited in the ?le of this patent Journal of Physical Chemistry, Brown et al., “Crystal line Intermediates . . . Calcium Polymetaphosphate,” vol. 61, July-December 1957, pages 1669 and 1670.