Patent GB-789446-A (GB)
Title: A process for the thermal decomposition of a metal nitrate and products made by the said process
IPC: C01B13/14
Filed: 1954-06-11
Abstract: Liquid nitric acid is obtained by the thermal decomposition of nitrates of metals other than aluminium, bismuth and iron and those which give rise to nitric oxide when decomposed, by decomposing the metal nitrate whilst spread over a metal or mineral surface, in the presence of steam in excess of that required to obtain nitric acid from the nitrogen oxides liberated, thereby obtaining a solid decomposition product and nitric acid vapours which are removed from the reaction zone and condensed. Thus the invention may be applied to the nitrates of Be, Ca, Cd, Ce, Cr, Co, Ga, Hg, In, Pb, Mn, Ni, Sn, Te, U and Zn to form oxides and nitrates of Ag, Au and Pt to form metals.  The nitrite to be decomposed may be applied as a coating on a granulated material or alternatively the molten nitrate may be spread out on a heated metal surface.  According to examples: (1) a manganese nitrate solution was fed to an internallyheated rotatable drum maintained at 190 DEG  C.; simultaneously air was sucked through the system for the removal of gases from the hot reaction zone and the gases containing nitric acid vapours were cooled down to room temperature in a condenser to obtain liquid nitric acid.  The manganese dioxide product was taken off from the drum by a knife. The nitrates of zinc, cobalt, nickel and chromium may be similarly decomposed; (2) lead nitrate was decomposed in a tube heated externally to 370 DEG  to 400 DEG  C. whilst blowing steam thereover. The steam and nitric acid vapours were condensed to liquid nitric acid and a yellow red oxide powder was recovered.  Mercuric and cadmium nitrates may be similarly decomposed.  (3) Calcium nitrate solution coated on sand was decomposed at 600 DEG  C.  Further granulated materials capable of acting as carriers are alumina, clay, infusorial earth or a recycled solid decomposition product. The coating of the carrier with the salt to be decomposed may be effected outside or inside the decomposition apparatus.  (4) A manganese ore was reduced at 400 DEG  to 500 DEG  C. to Mn2O3 and the reduced ore was treated with nitric acid at 60 DEG  C. to convert it to manganese dioxide solid and manganese nitrate solution.  The suspension was filtered and the solid precipitate was thoroughly washed and dried. The manganese nitrate solution was concentrated and introduced into a decomposition equipment as in (1) above which was supplied with heated air.  Further manganese dioxide was obtained and nitric acid was recovered in liquid form and could be re-cycled for the next batch operation. (5) A manganese ore was reduced at 500 DEG  C. to Mn3O4 and the reduced ore treated with nitric acid at 60 DEG  C. until one-third of the manganese had been converted to a hydrated manganese dioxide and two-thirds to the nitrate.  The suspension was filtered and the solid product containing about 70 per cent manganese dioxide was treated with a caustic potash solution to neutralize free manganic acid groups.  The manganese nitrate solution was concentrated and then decomposed at 200 DEG  to 300 DEG  C. as in (1) above.  The manganese dioxide obtained was freed from residual manganese nitrate by treatment with caustic potash solution.  (6) A manganese ore containing 35 per cent MnO2 and 4 per cent of iron was reduced by mixing the ore with a fuel oil and heating to 650 DEG  to 700 DEG  C. to form MnO.  The reduced ore was cooled and leached with dilute nitric acid to completely extract the manganese leaving the iron as insoluble.  After filtration the manganese nitrate solution so obtained was decomposed as before.  (7) Natural manganese carbonate (Rhodochrosite) was treated with dilute nitric acid and the insoluble suspension was neutralized with calcium carbonate in the presence of air, whereby dissolved iron and other metals were precipitated.  The manganese nitrate solution was filtered, concentrated and decomposed as before.ALSO:Gold, silver or platinum are obtained by thermal decomposition of their nitrates on a metal or mineral surface, in the presence of steam in excess of that required to form nitric acid with the nitrogen oxide liberated.