3,325,244 United States Patent Office Patented June 13, 1967

2 uses are in water treating and conditioning, or in manu 3,325,244 facture of water treating compositions. They may also be RaymondPASS; L. Copsoi, UM PYROPiHOSPHATE Syracuse, N.Y., assignor SOUTEON to Alied used as a base solution for formulating liquid fertilizers. Chemical Corporation, New York, N.Y., a corporation Pyrophosphates and tripolyphosphates are known com of New York pounds and are manufactured by heating alkali metal hy No Drawing. Fied Sept, 17, 1962, Ser. No. 224,242 drogen orthophosphates in the solid state at elevated tem 6 Cairns, (CE. 23-67) perature to drive off water of constitution, thus condensing This invention relates to potassium pyrophosphate So phosphate groups to form phosphoric anhydride linkages. lution and more particularly refers to a new and improved As an example of current practice, the steps in manu process for the production of a concentrated solution of O facturing a concentrated solution of tetrapotassium pyro potassium pyrophosphate suitable for use as a base for phosphate (TKPP) are as follows: heavy-duty liquid detergents. (1) A solution containing orthophosphoric acid Potassium phosphates generically embrace numerous compounds in which the individual compounds have dif (H3PO) ferent properties and uses. Illustrative of these potassiuin 5 is reacted with a solution containing potassium hydroxide phosphates are monopotassium orthophosphate (KOH) to prepare a solution containing dipotassium hy drogen orthophosphate (KHPO4). (KH2PO4) (2) The solution is dried to obtain solid dipotassium dipotassium orthophosphate (KHPOA), tripotassium or hydrogen orthophosphate. thophosphate (KPO), dipotassium pyrophosphate, (3) The solid is heated at 400 to 500 C. to drive off water of constitution, thereby causing condensation of two orthophsophate molecules to form one pyrophos tetrapotassium pyrophosphate (KPO), and higher chain phate molecule: phosphates having the general formula K2PO3x1 in which x represents a whole number of 3 or greater, as il 25 2K2HPO4(sold)- KAPO (solid) --H2O(gas) lustrated by the specific compounds potassium tripoly (4) The cooled solid product is dissolved in a limited phosphate (KPO10), potassium tetrapolyphosphate amount of water to obtain the desired concentrated solu tion. potassium pentapolyphosphate (KP5O16), etc. 30 Thus it will be evident that the conventional method of Two important commercial uses of potassium phos manufacturing TKPP solutions is cumbersome and com phate solutions are heavy-duty liquid detergents and liquid plicated and represents large investment and operating fertilizers. Potassium pyrophosphate is a preferred constit COStS. uent of such solutions because of its very great solubility An object of the present invention is to provide an effi (over 60% by weight of solution) and its good stability cient economical process for production of a concentrated in solution. Orthophosphates are much less Soluble. Mono solution of potassium pyrophosphate suitable for use potassium orthophosphate, KH2PO4, which is the solid as a base for heavy-duty liquid detergents, or for liquid phase in equilibrium with neutral orthophosphate solu fertilizers. Other objects and advantages will be apparent tions, has a solubility of only about 25% (by weight of from the following description. solution) at room temperature, and tends to 'salt out” 40 Superficially a most convenient method of producing when solutions containing orthophosphate are chilled potassium pyrophosphate solution would be by simple to low temperatures as in shipment or storage. In heavy mixing of a solution containing pyrophosphoric acid with duty liquid detergents, pyrophosphate is much more ef a solution containing potassium hydroxide. The difficulty fective in promoting detergency than is orthophosphate, lies in preparation of the solution of pyrophosphoric acid. and only minor amounts generally not more than 15% In U.S. Patent 3,022,154 of Feb. 20, 1962, a method and preferably less than 10% of orthophosphate by weight is described for producing a solution of potassium phos of the total potassium phosphate are desirable in making phates in which potassium hydroxide solution is mixed a good heavy-duty detergent. Higher chain phosphates, i.e. with "superphosphoric acid,” a liquid form of phosphoric potassium phosphates in which x of the general formula acid containing from about 75 to 77 percent P.O.5. Acid given above is 3 or greater, while having solubility and in this range of composition is a liquid mixture in which detergency characteristics comparable to pyrophosphate, about 56 to 40% of the total phosphate is present as are not as stable in solution. Whereas neutral or alkaline orthophosphoric acid, about 39 to 47 percent as pyro solutions of potassium pyrophosphate remain essentially phosphoric acid, about 5 to 11 percent as tripolyphos unchanged over a considerable period, higher chain po phoric acid, and up to about 2 percent as tetrapolyphos tassium phosphates in solution gradually hydrolyze, and 55 phoric acid. Corresponding to the composition of the as a result of such hydrolysis the orthophosphate content acid, the resultant potassium phosphate solution con of the solution gradually increases and may reach unde tained a mixture of phosphates, in which the pyrophos sirably high levels in a short time. phosphate.phate content amounted to less than one-half of the total Solutions of potassium pyrophosphates are useful in 60 The present invention is particularly directed to the the manufacture of heavy-duty liquid detergents, in which production of a concentrated potassium phosphate solu the potassium phosphate solution is blended with dissolved tion in which the major constituent is potassium pyro synthetic organic detergents and other additives. They phosphate and the solution contains less than 15% pref are also useful in manufacture of solid detergents. Other erably not more than 10% of potassium orthophosphate 3,325,244 3 4. by weight of the total potassium phosphate content in taining over 85% by weight of the total potassium phos the solution. - phates as potassium pyrophosphate with minor announts In accordance with the present invention a concen about 10% or less as potassium orthophosphate and trated solution of potassium phosphate containing as a about 5% or less as potassium chain phosphates higher major constituent potassium pyrophosphate and minor than potassium pyrophosphate. Such solution is emi amounts of potassium orthophosphate and higher potas nently suitable for use in heavy-duty detergents. We have sium polyphosphates can be produced by mixing liquid found that liquid acid containing about 79.8% POs can phosphoric acid containing 78 to 81% POs preferably be converted readily to crystalline granular pyrophos 79.8+0.5% PCs with a granular mass of previously pre phoric acid by agitating liquid phosphoric acid with a pared substantially solid pyrophosphoric acid, in the lO granular mass of previously prepared solid pyrophos proportion of 1-7 parts of solid per part of liquid phos phoric acid in any suitable mixer, e.g. a dry-type mixer, phoric acid, preferably 2-4 parts solid per part of liquid until the resultant product is a dry granular solid. To phosphoric acid, maintaining the temperature during mix initiate the reaction solid pyrophosphoric acid from an ing below 50° C. preferably within the range of 20-35 external source may be employed. Ordinarily the conver C. and continuing mixing until the resultant mixture is a sion to dry, granular solid will be accomplished in about substantially dry granular solid, returning a portion of 1 hour. It is important that the temperature of mixing said dry solid for admixture with additional phosphoric should not exceed about 50° C. or else a dry granular acid to produce additional dry solid, reacting the dry Solid will not result. Excess heat may be generated during solid with an aqueous solution of potassium hydroxide mixing and it is therefore advisable to equip the dry mixer containing about 40-65% KOH preferably about 50–57% 20 with suitable cooling means to control the temperature. KOH in the proportion of about 1 part of solid acid to Temperatures well below 50° C. may be employed but about 1.4-3.2 parts of KOH liquor, regulating the pro in practice it is not desirable to go below about 0° C. portion of said solid acid and potassium hydroxide so as Good results were obtained at a temperature within the to maintain the pH of said reaction mixture above 7.0 range of about 20-35 C. The amount of solid pyro and maintaining the temperature of the reaction mixture phosphoric acid should be at least equal to the amount during reaction within the range of about 20 to 110° C. by weight of liquid phosphoric acid and is preferably preferably within the range of about 45-70° C. about 2-4 times the quantity of liquid phosphoric acid. Phosphoric acid of high POs concentration may be A large proportion of solid pyrophosphoric acid may be obtained by dissolving solid phosphorus pentoxide (POs) employed but no material advantage is gained by using in ordinary commercial grades of phosphoric acid to 30 amounts greater than 6-8 times the quantity of liquid bring the concentration up to the desired range. It is phosphoric acid. A dry atmosphere maintained over the also possible to concentrate more dilute grades of phos mixer during the entire operation aids in preventing undue phoric acid in a vacuum evaporator. Phosphoric acid absorption of moisture by the acid. of the required composition can also be made in a phos The other raw material for the process of the present phoric acid plant in which electric furnace (elemental) invention is caustic potash liquor containing about 40 phosphorus is burned. Polyphosphoric acid containing 65% KOH preferably about 50–57% KOH. Temperature 83-84% POs as well as more dilute phosphoric acids of the liquor is that required to keep it from solidifying, are available commercially. In the process of the present and may range from room temperature for 55% KOH invention, liquid phosphoric acid containing 78 to 81% up to 110° C. or higher for 65% KOH. P2O5 preferably 79.8-h:0.5% POs is required. Acid of 40 The operation of the present invention may be carried this strength may be made directly by the methods pre Out in a batch or continuous manner. In a continuous viously outlined. However, if commercial acid of higher process, a stainless steel shaft mixer could be used, strength is used, the composition can be adjusted to that equipped with a water jacket for cooling. At the feed specified by addition of water, and similarly if more end, 1 part of liquid phosphoric acid containing 78 to dilute acid is available its concentration can be increased 81% P2O5 preferably 79.8-0.5% POs would be mixed to the desired range by dissolving solid phosphorus pent with 3 parts of recycled solid acid. At the discharge end oxide in the more dilute acid. the solid product would be divided with 3 parts being Liquid phosphoric acid containing from 78 to 81% recycled and one part going forward. P2O5 consists of mixtures in which pyrophosphoric acid Solid pyrophosphoric acid from the mixer, is then predominates. In this range about 30 to 11% of the 50 reacted with KOH liquor. Reaction may be continuous or total phosphate is present as orthophosphoric acid, about batch-wise. In batch operation, a charge of caustic potash 49 to 33% as pyrophosphoric acid, about 16 to 25% as liquor is placed in a mixing tank equipped with agitator tripolyphosphoric acid, and about 5 to 31% as tetrapoly and cooling coils. Solid pyrophosphoric acid is added phosphoric and higher chain acids. It is known that pyro gradually, mixing continued until the reaction is com phosphoric acid may crystallize at room temperature 5 5 plate. The finished pH value of the reaction mixture may from liquid acids in this composition range. It is also be in the range from about 7 to 13. Proportions are in known that these acids are "reorganizing liquids,' so that the range of 1 part solid acid to 1.4-3.2 parts of KOH when solid pyrophosphoric acid crystallizes the consti liquor the exact ratio depending upon concentration of tution of the residual liquor adjusts to restore a condition the KOH. Temperature and time are not critical but of equilibrium. Starting with liquid acid having exactly 60 typically the temperature is controlled at about 65° C. the P2O5 content of pyrophosphoric acid, namely 79.8% and mixing time per batch is about 1 hour. The finished P2O5, it is theoretically possible to convert completely to solution is cooled to about room temperature, and then Solid, crystalline pyrophosphoric acid. However, liquid Sent to storage, shipment or use. phosphoric acids in this composition range are viscous, The following example illustrates the present invention. syrupy liquids in which it is difficult to induce crystalliza Liquid polyphosphoric acid containing 83.4% POs tion. Once started, crystallization generally is slow and in was reacted with sufficient water to bring the composition complete. Separation of crystals from the viscous residual to 79.8% POs. About 15 minutes was allowed for reac liquor is difficult. Hence a practical, inexpensive process tion. About 20 parts by weight of the liquid acid was for production of pyrophosphoric acid or a solution of py added to the dry mixer which contained about 60 parts rophosphoric acid has not heretofore been available. We of Solid pyrophosphoric acid previously prepared, and have found a method of converting liquid phosphoric agitated for one hour at 30° C. About 20 parts of the acid containing 78 to 81% POs preferably 79.8--0.5% dry product was removed from the mixer, and added POs to a substantially dry, granular solid which solid gradually to about 52 parts of 50% KOH liquor in a wet when reacted with KOH liquor produces a solution con type mixer. The finished solution had a pH of about 13. 3,3 25,244 Chemical analysis of the solution is shown in columns 1 and 2 below: of 20-35 C. and continuing mixing until the resultant mixture is a dry, granular solid, returning a portion of the dry, granular solid for admixture with additional Physical Form of Acid Used liquid phosphoric acid to produce additional dry, granular Solid, admixing the dry, granular solid with an aqueous Solid Liquid Solution of potassium hydroxide containing about 50 57% KOH in the proportion of about 1 part solid acid Column to about 1.6-2.5 parts KOH liquor, regulating the propor tion of Said solid acid and potassium hydroxide so as 2 3 4 10 to maintain the pH of said reaction mixture above 7.0 and maintaining the temperature of the reaction mixture Percent Percent basis basis during reaction within the range of 45-70° C. Percent total Percent total in Soln. pot. in Soln. pot. 3. A method for the production of a dry, granular solid phos- phos acid composition composed essentially of pyrophosphoric phates phates 5 acid which comprises mixing liquid phosphoric acid con taining 78 to 81% POs with a granular mass of previ Potassium orthophosphate- 4.4 8 3.7 25 ously prepared solid pyrophosphoric acid in the propor Potassium tripolyphosphatepyrophosphate--- 48.3 89 24.5 44 tion of 1-7 parts of solid pyrophosphoric acid per part of and higher potassium liquid phosphoric acid, maintaining the temperature dur polyphosphates------Total potassium ... 6 3 7.6 3. 20 ing mixing below 50° C. and continuing mixing until phosphates------54.3 100 55.8 00 the resultant mixture is a substantially dry, granular solid, and returning a portion of the dry, granular solid for For comparison, columns 3 and 4 above show the analysis admixture with additional liquid phosphoric acid to pro of a potassium phosphate solution made by reacting liquid duce additional dry, granular solid. pyrophosphoric acid directly with KOH liquor. Thus, 4. A method for the production of a dry, granular when reacting solid pyrophosphoric acid with hot KOH solid acid composition composed essentially of pyro liquor in accordance with the present invention over 85% phosphoric acid which comprises mixing liquid phosphoric of the total phosphate in the product solution was present acid containing 79.8-0.5% POs with a granular mass as tetrapotassium pyrophosphate. Whereas when reacting of previously prepared solid pyrophosphoric acid in the liquid pyrophosphoric acid with KOH liquor there was 30 proportion of 2-4 parts of solid pyrophosphoric acid per produced a mixture of potassium phosphates in which part of liquid phosphoric acid, maintaining the tempera potassium phosphates other than potassium pyrophos ture during mixing within the range of 20-35 C. and phate constituted over 55% of the phosphates and the continuing mixing until the resultant mixture is a dry, potassium pyrophosphate content based on the total potas granular solid, and returning a portion of the dry, granu sium phosphate was only 44%. 35 lar solid for admixture with additional liquid phosphoric Although certain preferred embodiments of the inven acid to produce additional dry, granular solid. tion have been disclosed for purpose of illustration, it 5. A dry, granular solid acid composition composed will be evident that various changes and modifications essentially of pyrophosphoric acid prepared by mixing may be made therein without departing from the scope liquid phosphoric acid containing 78 to 81% POs and and spirit of the invention. 40 19 to 22% water with a granular mass of previously I claim: prepared solid pyrophosphoric acid in the proportion of 1. A process for the production of an aqueous solu 1-7 parts of solid pyrophosphoric acid per part of liquid tion of potassium phosphate containing potassium pyro phosphoric acid, maintaining the temperature during mix phosphate as the major phosphate constituent and only ing below 50° C. and continuing mixing until the resultant minor amounts of potassium orthophosphate and higher 45 mixture is a substantially dry, granular solid. potassium polyphosphates which comprises mixing liquid 6. A composition as claimed in claim 5 wherein the phosphoric acid containing 78 to 81% POs with a granu liquid phosphoric acid contains 79.8+0.5% POs and lar mass of previously prepared solid pyrophosphoric 20.2-0.5% water. acid in the proportion of 1-7 parts of solid pyrophos phoric acid per part of liquid phosphoric acid, maintain 50 References Cited ing the temperature during mixing below 50° C. and continuing mixing until the resultant mixture is a sub UNITED STATES PATENTS stantially dry, granular solid, returning a portion of the 1,336,974 4/1920 Levin ------23-139 dry, granular solid for admixture with additional liquid 1,815,581 7/1931 Pauckner et al. ------23-165 phosphoric acid to produce additional dry, granular solid, 55 2,128,182 8/1938 Fiske ------23-165 admixing the dry, granular solid with an aqueous solution 2,133,286 10/1938 Fiske ------23-109 of potassium hydroxide containing about 40-65% KOH 2,338,407 1/1944 Coleman et al. ------23-165 in the proportion of about 1 part solid acid to about 2,811,419 10/1957 Hartlopp et al. ------23-107 1.4-3.2 parts KOH liquor, regulating the proportion of 3,022,154 2/1962 Potts et al. ------71-34 said Solid acid and potassium hydroxide so as to main 60 3,057,711 10/1962 Reusser et al. ------71-43 tain the pH of said reaction mixture above 7.0 and 3, 192,013 6/1965 Young ------23-165 maintaining the temperature of the reaction mixture dur 3,228,752 1/1966 Hignett et al. ------23-107 ing reaction within the range of 20-110° C. OTHER REFERENCES 2. A process for the production of an aqueous solu tion of potassium phosphate containing potassium pyro Mellor, J. W.-"A Comprehensive Treatise On Inor phosphate as the major phosphate constituent and only ganic and Theoretical Chemistry," vol. 8, pp. 971–976, minor amounts of potassium orthophosphate and higher Longmans, Green & Co., London, 1947. potassium polyphosphates which comprises mixing liquid Shreve-'Selected Process Industries,” p. 323, McGraw phosphoric acid containing 79.8-1-0.5% POs with a Hill, Inc., New York, 1950. granular mass of previously prepared solid pyrophos 70 Van Wazer-"Phosphorus and Its Compounds, vol. phoric acid in the proportion of 2-4 parts of solid pyro 1, pp. 617-626, 770-777, Interscience, New York, 1958. phosphoric acid per part of liquid phosphoric acid, main OSCAR R. VERTIZ, Primary Examiner. taining the temperature during mixing within the range O. F. CRUTCHFIELD, Assistant Examiner.