Pennzoil Company

Erhart K Drechsel

John B Sardisco

Dysart E Holcomb

Ben E Adams

James R Stewart, Jr

Monocalcium phosphate, phosphoric acid and/or potassium phosphate, calcium fluoride and gypsum are produced in a process involving acidulation of phosphate rock with phosphoric acid, and wherein monocalcium phosphate dissolved in phosphoric acid is formed during acidulation. In important features, insolubles and impurities are removed and a portion of the monocalcium phosphate may be separated and recovered. Alkali metal ion is added to the solution to form alkali metal fluosilicate, such as K.sub.2 SiF.sub.6, is separated and hydrolyzed with calcium ion to form CaF.sub.2 and the solution is recycled as RH.sub.2 PO.sub.4 /H.sub.3 PO.sub.4 for further reaction with fluorides, where R is alkali metal. A portion of the MCP/H.sub.3 PO.sub.4 solution and/or crystallized monocalcium phosphate can then be reacted with potassium sulfate, potassium bisulfate, or mixtures thereof, to form KH.sub.2 PO.sub.4 or KH.sub.2 PO.sub.4 /H.sub.3 PO.sub.4 solutions, and gypsum or with H.sub.2 SO.sub.4 to produce phosphoric acid. The remaining monocalcium phosphate/phosphoric acid solution can be reacted with sulfuric acid to produce phosphoric acid product and the recycle phosphoric acid required in the phosphate rock acidulation step.

Preparation of monocalcium phosphate and/or phosphoric acid from

Phosphate rock, including low grade phosphate ore, is treated to recover phosphoric acid and other valuable products by a series of steps including contacting phosphate ore with a weak phosphoric acid to form a suspension of at least a portion of the slimes contained in the ore so that the slimes can be separated from the ore, and separating the slimes to provide a deslimed phosphate ore. Deslimed phosphate rock is solubilized with phosphoric acid to convert at least a portion of the calcium contained in the rock and form a solution of monocalcium phosphate and phosphoric acid. After removal of solids, this solution can be treated with sulfuric acid in a gypsum crystallizer to form gypsum and the phosphoric acid product wherein filterable gypsum crystals are obtained by maintaining a total SO.sub.3 content of 1.5-4 wt. % in a first crystallizer and neutralizing the SO.sub.3 in a second crystallizer. In other aspects of the invention, at least a portion of the phosphoric acid produced may be recycled to convert additional ore and the slime suspension may be treated to recover the weak acid recovered from the suspension. Further, wash water from the gypsum filter may be recycled to the desliming stage, the filtrate from the deslimer may be cycled to the acidulation reactor and monocalcium phosphate may be recovered as a separate product from phosphoric acid and connected to other useful products.

Production of phosphoric acid and additional products from phosphate ore

Alkali metal sulfates are produced from an aqueous solution containing alkali metal hydrogen sulfate which comprises contacting the aqueous solution of alkali metal hydrogen sulfate with a hydrophilic solvent, the hydrophilic solvent being effective to extract at least a portion of the sulfuric acid formed as the alkali metal hydrogen sulfate is converted to alkali metal sulfate in the solution, together with at least a portion of the water present; permitting the alkali metal sulfate solid to crystallize; and recovering the solid alkali metal sulfate product. The hydrophilic solvent may then be extracted and separated from the sulfuric acid with a hydrophobic solvent and both solvents can be recovered and recycled.

Production of alkali metal sulfates

Alkali metal-containing salt products selected from the group consisting of alkali metal dihydrogen phosphate, alkali metal sulfate, alkali metal nitrate, and mixtures thereof, together with alkaline earth metal fluoride, are produced from alkali metal fluosilicate by the steps of: (a) reacting alkali metal fluosilicate with alkaline earth metal ion in an aqueous solution to form alkali metal hydroxide and solid alkaline earth metal fluoride with SiO.sub.2 ; (b) separating the solid alkaline earth metal fluoride and SiO.sub.2 and recovering as useful products; (c) reacting the remaining alkali metal hydroxide solution with a mineral acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, and mixtures thereof, at a temperature in the range of about 30.degree.-100.degree. C. until the reaction is complete; and (d) recovering the alkali metal-containing product. Also provided by this invention is a continuous system for conducting this reaction whereby mother liquors may be recycled and the acid reused in the process, and wherein mineral acid is recovered from which anhydrous HCl can be produced.

Production of alkali metal products from alkali metal fluosilicate

Alkali metal fluosilicate is used as an intermediate reactant in a process for the production of hydrochloric acid and an alkali metal sulfate from sulfuric acid and an alkali metal chloride. The process includes the reaction of alkali metal fluosilicate with sulfuric acid to produce alkali metal sulfate and H.sub.2 SiF.sub.6, the latter being reacted with alkali metal chloride to produce HCl and alkali metal fluosilicate. The resulting hydrochloric acid may be converted to anhydrous hydrogen chloride. A continuous process for the production of hydrochloric acid and of alkali metal sulfate such as potassium sulfate from an alkali metal fluosilicate material is also disclosed.

Process for production of potassium sulfate and hydrochloric acid

A method is disclosed for the acidulation of phosphate rock and the production of substantially pure alkali metal phosphates, calcium phosphates, and phosphoric acid which are essentially free of fluorides and recovery of the fluorine values from the starting phosphate rock in useful form. The steps of the method comprise initial acidulation of phosphate rock with a phosphoric acid solution containing sufficient alkali metal values to provide R.sub.2 O in the system, where R is alkali metal, to solubilize the phosphates and form an insoluble precipitate comprising a mixture of impurities, sand (SiO.sub.2) and the fluorides, from which the fluorides can be recovered in usable form. In preferred embodiments, after removal of the precipitate containing the fluorides, a portion of the solution of phosphoric acid and calcium phosphate is reacted with sulfuric acid and RHSO.sub.4 or R.sub.2 SO.sub.4 where R is alkali metal, to form a solution of RH.sub.2 PO.sub.4 and phosphoric acid and at least a portion of the RH.sub.2 PO.sub.4 and phosphoric acid solution is recycled to the initial acidulation to provide the R.sub.2 O and phosphoric acid makeup. The remainder of the solution of calcium phosphate and phosphoric acid may be further processed for recovery of useful products such as monocalcium phosphate and/or dicalcium phosphate, phosphoric acid, alkali metal phosphates, and calcium sulfate.

Production of fluoride-free phosphates

Substantially fluoride-free phosphoric acid is produced by the acidulation of phosphate rock with sulfuric acid wherein the acidulation reaction is conducted in the presence of added potassium as K.sub.2 O bearing compounds, e.g. KHSO.sub.4, K.sub.2 SO.sub.4, KH.sub.2 PO.sub.4 or KOH, and additional silica, to precipitate fluorides and silica as potassium silicofluoride and then removed on separation of the gypsum formed. Optionally, additional silica may be added to the phosphoric acid solution recovered after precipitation and removal of the gypsum, to precipitate additional fluoride as potassium silicofluoride to further purify the phosphoric acid. In a further embodiment sufficient potassium may be added along with additional silica in the acidulation step to produce potassium dihydrogen phosphate and phosphoric acid as additional products. The phosphoric acid and potassium dihydrogen phosphate are recovered substantially free from fluoride contamination and the reaction is carried out in the substantial absence of fluorine evolution into the atmosphere. Also disclosed is a process for conducting a conventional phosphoric acid facility to produce phosphoric acid and gypsum wherein defluorination of the phosphoric acid recovered is achieved by silicon dioxide and K.sub.2 O addition and the fluorides are removed from the system, the process including steps for production of pure phosphoric acid and potassium dihydrogen phosphate.

Fluoride-free phosphate reactions

Monocalcium phosphate, phosphoric acid and/or potassium phosphate containing fertilizers are produced in a process involving acidulation of phosphate rock with phophoric acid in the presence of added silicon dioxide and potassium ion whereby fluorides contained in the rock are converted to K.sub.2 SiF.sub.6, wherein monocalcium phosphate dissolved in phosphoric acid is formed during acidulation. In an important feature, the K.sub.2 SiF.sub.6 is separated and hydrolyzed to regenerate the K.sub.2 O from K.sub.2 SiF.sub.6 as recycled KH.sub.2 PO.sub.4 /H.sub.3 PO.sub.4 solution for further reaction with fluoride from fresh phosphate rock feed. A portion of the MCP/H.sub.3 PO.sub.4 solution and/or crystallized monocalcium phosphate can then be reacted with potassium sulfate, potassium bisulfate, or mixtures thereof, to form KH.sub.2 PO.sub.4, or KH.sub.2 PO.sub.4 /H.sub.3 PO.sub.4 solutions, and gypsum. In a closely related embodiment, the remaining MCP/H.sub.3 PO.sub.4 solution is reacted with sulfuric acid to produce phosphoric acid product and/or the recycle phosphoric acid required in the phosphate rock acidulation step.

Preparation of monocalcium phosphate and phosphoric acid

Substantially fluoride-free phosphoric acid is produced by the acidulation of phosphate rock with sulfuric acid wherein the acidulation reaction is conducted in the presence of added potassium as K.sub.2 O bearing compounds, e.g. KHSO.sub.4, K.sub.2 SO.sub.4, KH.sub.2 PO.sub.4 or KOH, and additional silica, to precipitate fluorides and silica as potassium silicofluoride and then removed on separation of the gypsum formed. Optionally, additional silica may be added to the phosphoric acid solution recovered after precipitation and removal of the gypsum, to precipitate additional fluoride as potassium silicofluoride to further purify the phosphoric acid. In a further embodiment sufficient potassium may be added along with additional silica in the acidulation step to produce potassium dihydrogen phosphate and phosphoric acid as additional products. The phosphoric acid and potassium dihydrogen phosphate are recovered substantially free from fluoride contamination and the reaction is carried out in the substantial absence of fluorine evolution into the atmosphere. Also disclosed is a process for conducting aconventional phosphoric acid facility to produce phosphoric acid and gypsum wherein defluorination of the phosphoric acid recovered is achieved by silicon dioxide and K.sub.2 O addition and the fluorides are removed from the system, the process including steps for production of pure phosphoric acid and potassium dihydrogen phosphate.

Method of producing phosphoric acid and potassium dihydrogen phosphate

In a process for the reaction of phosphate rock and sulfuric acid in the presence of potassium ion to form a mixture of phosphoric acid and a precipitated gypsum wherein the presence of the potassium ion causes precipitation of fluorides from the phosphate rock as potassium silicofluoride as a coprecipitate with the gypsum, and the phosphoric acid is separated from the gypsum slurry, the potassium silicofluoride is separated from the gypsum by extraction with phosphoric acid which may contain from 0-25 weight percent of sulfuric acid based on the amount of gypsum to be extracted or such phosphoric acid which may contain some fluorine. This extraction procedure provides a substantially fluoride-free gypsum product and an extraction solution containing recoverable potassium silicofluoride.

Recovery of fluorides from gypsum

Method of producing fluoride-free phosphoric acid

Potassium sulfate (K.sub.2 SO.sub.4) is prepared by contacting potassium chloride with an aqueous solution containing potassium bisulfate at a temperature of about 65.degree.-110.degree. C., cooling the solution and permitting the potassium sulfate to crystallize from solution.

Manufacture of potassium sulfate

Potassium phosphates useful as fertilizer materials, are produced by the reaction of phosphate rock or a solubilized form thereof, concentrated sulfuric acid and potassium hydrogen sulfate wherein the potassium hydrogen sulfate is added in a controlled manner and preferably in admixture with at least a portion of the sulfuric acid, the precipitated calcium sulfate precipitate is removed and the filtrate processed for recovery of the potassium phosphates. In further embodiments, high-sulfate containing filtrates are treated to lower the sulfate ion content of the products and effect partial neutralization by any of several methods such as by treatment thereof with fresh phosphate rock or source of calcium ion such as calcium oxide, alternatively or successively, and the resulting solution is used as a fertilizer, or liquids are removed and the solids are dried and/or dehydrated for recovery of the potassium phosphate compounds. Also methods are provided for the addition of nitrogen values.

Growing community of inventors

Houston, TX, United States of America

Erhart K Drechsel