Patent GB-1049197-A (GB)
Title: Process for preparing phosphoric acid and phosphates from raw phosphates decomposed with nitric acid
IPC: C01B25/22
Filed: 1963-11-05
Abstract: A rough separation of calcium nitrate from the acids in a solution obtained in nitric acid decomposition of phosphate rock is achieved by extracting the greater part of the phosphoric acid and nitric acid from the solution with a polar organic solvent, or a mixture of polar organic solvents, having limited miscibility with water, leaving the greater part of the calcium nitrate and a small amount of the acids in the aqueous phase.  The organic phase, containing say 5 to 20% of the Ca content of the rock, may be subjected to extraction with water in a multi-stage system to yield firstly an aqueous solution of Ca(NO3)2 and secondly a solution of H3PO4 and HNO3, apparatus of the type shown in Fig. 1 being employed.  Nitric acid of strength, say, 40 to 55%, and phosphate rock, i.e. basic materials containing Ca3(PO4)2, are fed from tanks 1 and 2 respectively to decomposition reactor 3 in proportion, e.g. 23 moles. of HNO3 to 3 moles of Ca3(PO4)2. The resulting solution flows into settling tank 4, which may be supplied with NH3 through conduit 5, where all undissolved constituents precipitate and may be discharged.  The solution of Ca(NO3)2, H3PO4 and HNO3 passes into extraction column 6 and is washed in counter-current relation with an organic solvent, say an aliphatic alcohol, ketone or ether or a mixture of such solvents, which may contain a small amount of water and HNO3, the volume ratio of organic solvent to solution being at least 1:1 and the extraction temperature, e.g. less than 60 DEG  C.  The resulting aqueous phase, containing the greater part of the Ca(NO3)2, is discharged into column 7 where it is freed of organic solvent, which is recycled through conduit 32, and subsequently discharged through conduit 8, say to an apparatus for preparation of Ca(NO3)2 fertilizer.  The organic phase, containing H3PO4, HNO3 and Ca(NO3)2 passes from column 6 to extraction columns 10, 11 and 12 in turn, where it is washed with water supplied from tank 13 through conduit 14, the ratio of the total volume of water used : volume of organic solvent being, e.g. 1:4 to 6.  Ca(NO3)2 solution is discharged from the bottom of the columns and returned through conduit 15 to column 6. The organic solvent, containing virtually only HNO3 and H3PO4, passes through conduit 16 into column 17, where it is washed with, say, 1 part by volume of water per 2 to 4 parts of solvent and then passes through conduit 18 to vessel 19 where its pH is adjusted to about 3 with NH3 from conduit 20 and subsequently to separator 21.  Phase separation results in an aqueous bottom layer containing (NH4)3PO4 and NH4NO3 and a top layer of organic solvent and residual water, which may be recycled through conduit 22, storage vessel 23 and conduit 24 and acidified through conduit 34.  The bottom layer passes into column 10 via buffer vessel 25 and conduit 26.  An aqueous solution of H3PO4 and HNO3 passes from the bottom of column 17 through conduit 27 and may be processed to H3PO4 by stripping off residual organic solvent in column 28, the solvent being recycled through conduit 33, and passing it through conduit 29 to apparatus for removal of water and HNO3 by distillation. alternatively, if the final object is production of a fertilizer containing nitrate and phosphate, the salt solution collected in vessel 25 may be passed into column 17 through conduit 35 and the solution discharged from the bottom of this column passed into neutralization vessel 31 through conduits 27 and 30, stripped of residual solvent in column 28 and passed through conduit 29 to evaporating and granulating equipment. If an NPK fertilizer is desired, the solution leaving the bottom of column 28 may be used, with additional HNO3, to convert KCl into KNO3 and the resulting solution neutralized with NH3, evaporated and granulated.  In the modified process represented in Fig. 2, the organic phase discharged from column 6 passes directly to column 17 where both the acids and the Ca(NO3)2 are washed from the solvent with a solution of NH4NO3 and (NH4)3PO4 from conduit 35.  The resulting solution, of composition, say, 3 moles HNO3 and 2 moles Ca(NO3)2 per 6 moles of H3PO4, discharged via conduit 27 may be processed as follows.  After removal of organic solvent in column 28, the solution passes to vessel 31a where its pH is raised to about 2 with NH3.  About 1/4 of the Ca content forms CaHPO4.2H2O contaminated with CaF2, and this is filtered off in apparatus 36 and returned through conduit 37 to vessel 3. The filtrate passes to vessel 39 where its pH is raised to about 6 with NH3 and the remaining Ca is precipitated as CaHPO4.2H2O which is filtered off in apparatus 40, washed with water in tank 41 and filtered in apparatus 42.  The product obtained, CaHPO4.2H2O containing 0.1 DEG  F, is discharged through conduit 43 and the wash water is passed through vessel 25 to column 17.  The filtrate from apparatus 40, containing NH4NO3 and NH4H2PO4, passes to evaporator 46 and subsequently to a granulating device, the resulting product being an NP fertilizer. Alternatively, the solution discharged through conduit 27 is passed through conduit 30 to vessel 31 and neutralized with marl until the CaO:P2O5 ratio is 2:1 before removal of organic solvent and further neutralization. This modification results in production of CaHPO4.2H2O containing 0.05% F. and of a fertilizer containing only NH4NO3 as nutrient. When neutralization in vessel 31a is omitted, the CaHPO4.2H2O obtained has a higher F content. The extraction columns employed may be packed or plate-type, the liquids preferably being subjected to pulsation.