The Electrolytic Recovery of Silver from Photographic Fixing Baths

"Photographic technology is based on light sensitivity of silver halides that, because of silver properties, are capable of forming photographic images. Photographic laboratories and hospital departments because of digital photographic systems less use this technology today. Nevertheless recovery of silver is still advantageous because environmental problems related to Ag ions danger to biological system. Many processes have been studied to treat silver containing photographic bath: cementation, chemical precipitation and electrowinning. In this work, after preliminary voltammetric tests, a batch electrometallurgical process has been studied to completely deplete the silver containing photographic fixing baths. The effect, of silver concentration in the electrolyte, varying over the range 0,2-1 g/L, bath stirring and current density ranging from 10 to 500 A/m2 on process yield and deposit quality, has been investigated. Introduction Photographic wastes, electronic scrap and spent catalysts constitute the main sources of materials for silver recycling. Among those silver secondary sources, the photographic discharged material could be still important and useful, even if photographic laboratories and hospital departments, because of digital photographic systems, less use photographic technology. Several processes have been developped in order to recover silver used in the field of photography from both photographic solutions and scrap film paper[1-5]. Fixing solutions are very complex baths but, because of silver position in the electromotive series, electrolysis could represent an advantageous method for silver recovery. Electrolysis produces high purity silver without generating new pollutants, while the fixer can be reused: obviously it is necessary to purge off a portion of this solution in order to avoid the excessive build up of other deleterious compounds into solution. A tested recovery method was constituted by the dissolution of silver from X-ray films with concentrated nitric acid. Internal electrolysis and external electrolysis methods were carried out using a steel electrode as cathode and a copper electrode as anode [6]. Silver recovery from photographic chemical solutions has been also performed in a special cell [7]: the solution is supplied to the bottom of a non-agitated cell having a vertically elongated form and including a central anode enclosed by a cathode. An other study discloses the use of an electrolytic cell comprising at least one anodic compartment and one cathodic compartment: the solution is treated in the cathodic compartment and then recycled in the anodic one [8]. A more recent work proposes the use of zirconium cathode for the recovery of silver from photographic fixing solution [9]: studies carried out by cyclic voltammetry showed that about 98% of total Ag can be recovered with an electrical efficiency close to 92%."