CLEAN TECHNOLOGY FOR TREATMENT OF PHOTOGRAPHIC WASTES AND SILVER RECOVERY S. Jeyaseelan* and S. Sathananthan** *Schoot of Civil and Structural Engineering Nanyang Technological University, Singapore **Department of Buildings Ngee Ann Polytechnic, Singapore ABSTRACT: Photographic industry which is extensively used by the medi heavily depend on silver. The industry produce large quantities of wastewater containing high concentrations of sliver compounas. siver in all forms i regavied as toxic heavy metal dn pronmstod from discharging into public sewers. Also silver ix an expensive commodily and recovery of sliver from these wastewaters and recycling improves production cost. Thus makes the process an eovironmentally fiiendly operation. This paper gives an insight of an improved silver extraction process developed at the building department of Ngee Ann Polytechnic to effectively recover silver feom photographic wastes and to treat the waste water to standards acceptable for disposal, by the Ministry of the Environment, 1, Introduction For decades photographic industries have played a major role in man's life. Medical and film industries extensively use high quality photographic films and X- ray films. Photographs consisting images of people brings back memories and with the development of highly technical cameras with easy handling techniques of them, photographs are taken in every small occasion in the modern societies. The word "Silver" will also remind people accessories like necklace, bracelets, rings etc. ‘The photographic industry is a prime example of an industry that depends heavily on silver. Nothing has been found to equal it as a light sensitive material capable of forming photographic images because of the unique qualities of silver. Pera and Mexico are the largest silver producing countries in the world and photographic industries are its largest consumers. Like many of our natural resources, it is rapidly diminishing in availability, The cost of silver has risen considerably in recent years mainly due to price increase on the international market compounded with a world shortage of silver. Fortunately, much of the silver used by the photographic industries can be recovered and reused. Unlike other natural resources, the silver used in the photographic process is not destroyed by its use. Environmental Monitoring and Assessment 44: 219-229, 1997. ©1997 Kinwer Academic Publishers, Printed in the Netherlands.220 S. JEYASEELAN AND S. SATHANANTHAN SOURCES OF SILVER Silver in the photographic industry is recovered from two main sources: photagraplic solutions and scrap filins. Dasically two typos of solutions acc used in the photographic industries, they are the fixer and bleach solutions. The fixer solutions consists of chemical substances that have the ability to dissolve sensitized salts on films on which photographic inages could be developed. Tixer solutions dissolve the opaline silver compounds on the film and cause the picture to remain unchanged when exposed to light, Bleach solutions are used to rinse the negatives on which the photographic images are founed. The photographic wastes which comprises mainly fixer and bleach solutions, contain high concentrations of dissolved silver and other chemicals such a3 Sutphates and Nitrates. Silver, in all forms, is regarded as toxic heavy metal, as a result, wastes generated in the photographic industry are considered as hazardous waatea and are prohibited from discharging into the public sewers. OBJECTIVES OF THE PROJECT This project was undertaken with the collaboration of a company, who are the Ministry of the Environment approved disposal contractors for photographic wautes. This sompany vollocts photographic wastes from photo labs, printing presses and hospitals in Singapore. The paper records the summary of the experimental findings, a comparison of the merits of the electrolytic process of cilver recovery, and miggections: for an improved wacte wator treatment cyctem for the company. 2, Methods of Extraction of Silver The mathod employed for the vatruction of cilver from photographic wacte ie bared on electrolysis, When a direct current is applied between two electrodes immersed in a container bearing photographie waste solution, metallic silver would deposit on the cathade. The cathode could be removed periodically and the silver deposits could he stripped off, The main advantage of the electrolytic recovery method is that the silver obtained is of very high purity. It is 4 clean system evolving no gases and generating no new pollutants. However the electrolytic silver extraction process could be influenced by several environmental factors, These were critically examined at the laboratories. and the observations are as follows: a Agitation: Sulphating ean occur, even in high concentrations if the solution in the immediate vicinity of the cathode becomes depleted of silver.Cathodes must be in continuous contact with frech silver laden salution, Ta prevent euiphating, continnans agitationCLEAN TECHNOLOGY 221 is necessary. The greater the physical agiuuion the beuer ine reaction erviciency to produce metallic silver, Greater agitation also allows higher plating current to be used. However agitation should not be so violent as to cause splatter, spill over or eaueas Cvapuiall b. Silver Content : Higher silver coment uicans une dissvlved silver will be in wie vicinhy of une cathode and therefore higher current density can be used. The colour of the deposit is a good indicator of the plating conditions. c. Plating current: A plating current in the range of 7.5 Amps to 9.0 Amps could be used, When plating current is much less then, thy silver deposit will be hard aud Geamy white. At optimum current of 9 Amps the colour of the silver deposit will be dark grey and granular. The lower the current, the finer the silver deposits are obtained. d. pH: The pH of the waste solution could be between 4.2 to 5.0. However the optimum value for beat silver recovery is 4.5. e. Sulphate Concentration : Sulphate suppresses the formation of fi eo osulplur. Sulplates ae vuusuiued ia Ue electrolysis and must be replaced. Maintaining a steady state concentration of 7 to 10 g/l is necessary for efficient silver recovery, Sulphate concentration seems to be important for Ammonium thiomilphate solutions. This replenishment takes place in the anode itself. The most prevalent reaction at the anode is the oxidation of sulphite to sulphate. Experimentations indicated that approximately 1 gram of Sadium Sulphits ie oxidised for caeh gram of) iver recovered, f. Plating Aids : A plating aid depocite in trace amounts and adherent. Gelatine is one of the best aids and is always present in ample amounts in photographic wastes, coming from the film itself. silver males the silver deposits firm: g. Chemical Contamination : Oil or other chemicals on the cathode will cause poor silver deposi h, Surface Area of Cathod ‘The larger the surface area of the cathode, the more silver will be deposited. However the surface area of the cathode must face the Carhon anode and the spacing between the anode and cathode should be 25 to 30 mm. i. Operating Time : There is no limit for the operating time duration. However the time factor is dependent on the plating current, and the silver contents in the solution. Investigations reveul that a six hour eyele with a plating current of 9 Amperes is found to be reasonably economical for optimum silver extraction. Prolonged222 S. JEYASEELAN AND §. SATHANANTHAN ON/OFF ON /0; swics Ga VOLTAGE ) y RECULATOR P o | AMMETER To ANODE 40 CATHODE ‘MOTOR (N) MOTOR (2) TRANSFORMER KACTIFIER LIVE NEUTRAL BARTH FAN CIRCUIT LAYOUT Fig. f | > METAL OPED ro raga | POSITIVE CURRENT we, 100, 100, 180 _, 100 , 100 a - 100 ~ 100 Cl | 400 L. —_ tL é-----------= See} ANODE (Carson) PLAN VIEW ANODE CIRCUIT UNIT IN Mat Fig. 2CLEAN TECHNOLOGY 223 operation beyond six hours was tound to have no significant improvement in the quantity of silver recovered. CONSTRUCTION DETAILS FUK [HE RECUVERY UNL The Figure 1 illustrates the electrical circuit developed for the silver extraction uni, As shown In the rigure, the live cable from the main supply are connected to an MCB and a tripping device, The power supply is then split into two through two cables, one to the motor and other to the voltage regulator. From the voltage reguluior, the live cable Is connected (0 the transformer input. |he carbon anode was connected to the transformer output along with an ammeter. Several improvements were incorporated in the unit for silver extraction, ihe surface area of the cathode was increased by having two cylinders as cathodes as shown in figure 2, each capable of accumulating seven kilograms of silver. The cathodes and all ine) components included in the unit were made of 316 stainless. steel to prevent corrosion of the components due to the acidic and corrosive photographic waste solution, The anode surface area was also proportionately inuicascd. Sia carbon plates were placed in the comainer w faciliuie greater ton exchange. A bridge rectifier was used to reduce the heat generated, Carbon brushes were used for the contacts to minimise sparking. As a safety feature a tripping device was installed wunnecting die live cable wan MCB ww prevent une cover being accidently opened during operation. EXISTING TREATMENT METHOD OF WASTE WATER Tor silver seuvery puipuses it is Cunvenient wo process ure bleach soluuion and fixer solution separately. This is necessary because the environmental conditions required for silver recovery for both solutions are different, particularly the plating current, Wher the silver iu the phutugraphic wane is adequately ievuvered, ie waste water will have to be treated to acceptable standards before discharge. The company operates a treatment plant to treat the waste water, [lowever the company face several problems in treating the waste. Table 1 shows the results obtained from tests conducted on waste samples taken straight after the recovery of the silver. No chemicals or substances wore added to improve the condition of the wastes. Table 2 shows the limits on various water quality parameters stipulated in the Trade Effluent Regulations 1977 by The Ministry of the Environment, Singapore. From the results it is clear the most problematic parameters are the COD with a concentration of 63,000 mg/l, Total Dissolved Solids with concentrations of 57,334 mg/l and colour. Photographic wastes are inorganic in nature. It would be inappropriate to use biological m to treat the wastes, Furthermore, the cost of the treating the wastes need to be considered as a factor influcncing the choice of a particular treatment method.224 S. IEYASEELAN AND S. SATHANANTHAN Table 1 Properties of Photographics Wastes ig), Nip, won IER mA stugce stuone FILTERS, wasre cocecriaN SUMP SCEMETIC DIAGRAN SHOWING THE TREATMENT PROCESS USIKG 202 TREATED WATER Brrer! Reference source BLEACH FIAER MIX not found. PARAMETERS Total Sugpandad Salide (mai) AAA 205 268 Total Dissolved Solids (mg/L) 56940 55400 | 57334 ‘Tuual Volatile Solids Ung/Ly 48087 48149 45110 Total Fixed Solids (mg/L) 9297 9880 | 9588 Chemical Oxygen Demand (mg/L) 33600 54400 | 63500 Sulphate (mg/L) 712 512 612 Nitrate (mg/L) 4.14 2.80 3.47 pH value 5.30 4.26 4.78 Colour (Hazen) 2250 2250 | 2250 Turbidity (nest) 80 90, 270 24 on | schbnuen coer Lj-— TREATED watER HOLDONG TANK WATER COLLECTION SuNP Fig. 3CLEAN TECHNOLOGY 225 Table Z Trade Efftuent Regulation Limits Error! Reference source not Timite found. PARAMETERS Total Suspended Solids (mg/L) 400 Total Dissolved Solids (mg/L) 1000 COD (me/L) 600 ph value 6-9 Sulphate (mg/l.) 600 Table 3 COD values with Contact Time and Ozone dosages Ozone COD (mg!L) | COD (mg/L) | COD (uny/L) Contact time | Dosage Trial | Trial 2 Average (min) (mg/L) 9 0 64,000 65,500 64,250 5 83 44,500 46,000 45,250 | 10 167 22,000 23,000 22,750 1s 230 12,000 13,000 12.500 20 333 8,000 8,500, 8,250 8 ALT 6,200 8,000 7,100 30 500 5,800 6,200 6,000 35 583 5,500 5,900 3, /90 40 667 4,000 5,000 4,700 45 150 100 4,400 4,250 50, 833 4,000 4,200 4,100 55 917 4,000 4,000 4,000 60 1000 3,800 4,000 3,900226 S. JEYASEELAN AND S. SATHANANTHAN Piguie 9 illustates the layout of dhe Weauuent wits used by the company, Lime powder is added to adjust the pH to about 10 to 11. Stirring for 1S - 20 minutes results in the liberation of free Ammonia and the formation of sludge. The free Auunuuia is saubbed uff by the fume serubber above the tauk, The sludge is dien drained to the dewatering unit for shidge dewatering. The filtrate is returned back to the sump for further treatment. Dilute Sulphuric acid is added into the clear water to adjust the pll te aluut 4 lu 6, Pive percout Tydieyen poivaide is uicu added into the clear water in the treatment tank and stirred for 30 to 45 minutes. This is to decompose thiosulphate to sulphite followed by sulphur oxidation to tetrathionate and then to sulphate. The complete acti and a drop in pH between 1.5 and 2.0. The pH is again adjusted to approximately 7.0 by the addition of sodium hydroxide. The supernatant is decanted into the treated water collection sump. Hos ine sludge fornsation Basically the treatment is using Hydrogen peroxide to reduce the COD and TDS contents before the waste water is discharged inte the public sewer. Although die treatment reduced the COD substantially,the treatment had several drawbacks. When lime powder is added to the waste water, ammonia gas is released. High concentration of Ammonia gx iv toxic. Thus the ataff involved in the treatment process found it uncomfortable. A fume scrubber is required to scrub off the ammonia released in the reaction, Every stage of the treatment there is a depression in the pH valuo. Tho chomical roaction botwoen Hydrogen peroxide and Thiosulphate is exothermic in nature, as a result substantial heat is generated during the addition of Hydrogen peroxide. Several chemicals, Hydrogen peroxide, Coleium hydroxide, culphurio aoid and Sodium hydronide are uacd in the troatment. Most importantly the company finds the overall cost for this elaborate treatment too high. The Company was keen to look into other alternate methods. PROPOSED TREATMENT METHOD OF WASTE WATER Investigating the company's treatment method it was oboorved that before the treatment the waste water from bleach solution and fixer solution and wash water from the plant were drained into a common sump, as indicated in the line diagram of the treatment process. The COD for bleach solution was 33600 mg/l and fixer solution was 54400 mg/l. When hath solutions were mixed the COD for the mixer was found to increase to 63500 mg/l, while other chemical parameters remained without any significant change. This increase in COD value may be attributed to the formation of chemicals during the mixing process. It could also be due to the solids in the wash water form the plant drained into the same sump. Mixing of wastes caused an increase of approximately 15% of the COD value. This increase could be avoided by separately collecting and treating the bleach solutions and fixer solutions. Ozone treatment was proposed as an alternate to the existing treatment method. Tahoratory investigations also indicated that ozone could be effective in theCLEAN TECHNOLOGY Table 4 Effluent Qualities with Ozone Treatment 27 PARAMETERS Colour Turbidity TDS (Hazen) (NTU) (mg/L) Fixer (Original) 2250 2.7 : Bleach (Original) 2250 80.9 - Combined Wactee 1250 24.0 SAAQ (Original) Duration of Ozone Introduction 5 mins 2000 15.8 48916 13 mins 2000 92 48314 30 mins 2000 19 37046 60 mins 2000 73 28391228 §. JEYASEELAN AND S, SATHANANTHAN Treatment Of photographic wastes. An Uzone generator Model KXAU-4 capable ot generating 2000 mg of Ozone per hour was used. Table 3 shows the results of the values of COD. Table 4 shows colour, turbidity and TDS during the introduction of Ozone int the photographic waste. From the Table 3, it can be observed that the average COD value was brought down 10 6000 Ing/t in 30 Infnutes, and with 6O minutes of Ozone introduction the average COD value was brought down to 3900 mg/l, The Total Dissolved Solids (TDS) was brought down to 28390 mg/l with 60 minutes of Ozone introduction. The Bleach sulutiun which lad a high wuibidity of 60 INTU units was brougnt down to 7.3 NTU unit. However the Colour of the waste water decreased from 2250 Hazen to 2000 Hazen. This is not a significant decrease. The methods of reducing the vulour in photogiaphic wastes are currently being investigaied. Aluhough Ozone treatment has not achieved the desired results, it has proven to he a viable alternative to the existing treatment system. Ozone treatment is found to be a clean Geaiinent without producing sludge and evolving any LOxis gases, 3. Conclusions The findings of this project are encouraging and the following conclusions are made from from the bec vations. Electrolytic recovery method has proved to be a environmentally friendly recovery method for rvovery of silver fom photographie wastes. The italing cathode electrolytic unit developed in this project was found to recover silver effectively under controlled conditions. Apart from continuous agitation of the waste solution, plating current, plT and Sulphate Guncunsatis chemical parameters which warranting continuous monitoring for effective silver recovery. were found ww be impurtaut Ozone was found to be very effective in treating the photographic wastes. With 30 minutes of Ozone introduction a 90% reduction in COD and a 50% reduction in TDS was achieved. Further introduction of Ozone over and above 30 minutos duration did not inake a significant reduction in COD. However the Ozone administration was extended to 60 mimates due to compelling need to bring down the COD nearer to the ueceptable limits, Although Ozone is known to be effective in reducing colour in waste water, experiments have indicated,that Ozonation of photographic wastes only «achieved 25% reduction in colour. REFERENCES 1. SPSE Handbook of Photographie Science and Engineering. Interscience Publications. 2. Photographie Chemistry, Volume one - A Fountain Publication. 3. Recovery of silver from photographic wastesCLEAN TECHNOLOGY 29 Kodak Publication No J 10. 4. Sewage Procedures and requirements Sewaye Department, Environment Engineering Division Ministry of Environment (Singapore) 5. Proceedings of Second International Symposium on Ozone Technology. Montreal 1975. 6, ‘The Role of Ozone in Water and Waste water I reatment R. Pemy, A.B. Mclintyre, Selper Lid, London 1985. . Ozone Treatment and Industrial Wastewater, Pollution Technology Review; No 84 Noyes Data Corporation 1991. . Removal of Metals trom waste water. George C Cushie Jr. Noyes Publications 1984. ¥Y, Ozone manual for water and waste water treatment. Dr.W.J.Masschelein, John Willey publication. o