Patent GB-975073-A (GB)
Title: Improvements in pigmentary silica
IPC: C01B33/18
Filed: 1962-04-24
Abstract: <PICT:0975073/C1/1> Silicon tetrafluoride is generated by passing a gaseous mixture of H2O vapour and 30-40% HF by weight through a pervious bed of crystalline siliceous material maintained at above the boiling point of water and below 430 DEG  F., and withdrawing the resultant mixture of SiF4 and water vapour.  The influent gaseous mixture is preferably passed at about 0-5 lb. HF/min./cu. ft. siliceous material.  The siliceous material may be quartz, tridymite or cristobalite, and may be as gravel or sand.  Pigmentary silica may be prepared by hydrolysis of the above effluent gaseous SiF4/H2O mixture.  A stream of this mixture is thoroughly mixed with a gas containing free oxygen and a gaseous fuel under conditions of extreme turbulence without substantial combustion, and thereafter burning the mixture. The resulting suspended silica is removed while the suspension and any walls with which it may make contact at above the dew point of the water vapour.  The separated silica may then be heated to remove residual fluorides therefrom. From the effluent gases an aqueous solution of 30-40% HF may be condensed and absorbed, and recycled to a vaporizing chamber.  In Fig. 1, crystalline silica in hopper 3 is charged to SiF4 generator 1.  Aqueous HF is recycled via line 6 to vaporizer 8, and gaseous HF/H2O mixture passes therefrom via line 9, superheater 10, and line 11 to SF4 generator 1, through which it passes upwardly in contact with the silica bed, the HF thus being converted to SiF4/H2O vapour mixture.  From 1 the SiF4H2O mixture passes through solids separator 13 to hydrolysing unit 2, the effluent therefrom passing via cooler 70 to electric precipitator 74, cyclone separators 76 and 77, and optionally bag filter 78.  The gaseous mixture and any residual silica then pass via line 81 or 81a  to absorber and fractionating column 82.  Any residual SiO2 and SiF4 will, as the gases pass upwardly through the descending water, be converted to H2SiF6 by reaction with HF.  To adjust the concentration of the aqueous HF solution, condensate passes via lines 86 and 87 to reboiler 88; the heated or vaporized condensate returns via line 87a  to column 82.  Aqueous HF of appropriate condensation then passes via pump 94 to line 6, whence it is recycled to vaporizer 8; it may also pass, for temperature regulating purposes, to generator 1 via line 35.  Collected pigmentary silica passes from the separator hoppers via pneumatic conveyer 96 to separator 97, and hence to treater 105 wherein it is heated to 500-1500 DEG  F. and residual HF is removed. In hydrolyzing unit 2, the SF4/H2O vapour mixture enters tangentially via line 16 a stream of preferably heated air in the form of a cyclone from chamber 44, and from injector 46 fuel gas enters radially the swirling SiF4/H2O/air mixture. The walls of hydrolyser 2 are cooled by air which may be withdrawn at 115 and injected as combustion air at 44. The pigmentary silica has mean particle diameter of 10-20 mm , oil absorption 25-50 gallons oil per hundred lb. silica, uncompressed bulk density 1-5 lb./cu. ft., surface area 120-220 m.2/g., S.G. slightly greater than 2, and contains at least 99% SiO2. Specification 779,804 is referred to.