Abstract:
A method to improve the functioning of a membrane of a nanofiltration device provided to filter a solution optimizes the retention rate of the membrane. In the method, the permeate and the retentate are circulated through the nanofiltration membrane for a time before starting to use the membrane. The method is applicable to the treatment of photographic baths.

Description:
FIELD OF THE INVENTION 
     The present invention relates to a method of improving the functioning of a membrane of a nanofiltration device, and in particular to improving the functioning of a membrane utilized in a treatment method of a photographic bath. 
     BACKGROUND OF THE INVENTION 
     Many manufacturing or processing methods produce wastewater that, on the one hand, cannot be cleared directly into drains because of their composition and, on the other hand, contain precious substances whose recovery and reuse may have economic advantages. One may cite the example of the photo processing industry, where exposed photographic films and papers go through several treatment baths, after which the chemical products must largely be removed from the finished products. Such treatment methods for photographic films are well known (e.g. see,  Chimie et Physique Photographiques ; Pierre Glafkides; Vol. 2; Chap. XL, pages 947-967). 
     It is common to use systems for treating and recycling the wastewater, in particular nanofiltration devices. Nanofiltration is a technique utilized for the selective separation of salts and organic compounds in solution. The membranes used for nanofiltration thus behave like sieves with a large area having microscopic or molecular size pores whose dimensions have to be very even in order for the molecules of a given size to be retained, while smaller molecules or the ions of simple salts pass through the membrane. Membranes for nanofiltration usually let pass molecules whose molecular weight is between 200 and 1,000 daltons. Multivalent ionized salts and non-ionized organic compounds with molar mass more than 1,000 daltons are, however, largely retained. The solution that has crossed the membrane is called the filtrate or permeate and the solution that is retained by the membrane is called the concentrate or retentate. 
     Nevertheless, it has been noticed that the retention rate of membranes is not optimal during treatment, i.e. a not insignificant amount of substances to be filtered is found in the permeate. This problem is especially important in the nanofiltration systems utilized discontinuously, provided to treat different batches of solution. 
     SUMMARY OF THE INVENTION 
     An object of the invention is to provide a method to improve the functioning of a membrane of a nanofiltration device provided to filter a solution so as to optimize the retention rate of a membrane. 
     The invention relates to a method to improve the functioning of a membrane of a nanofiltration device provided to filter a solution, in which the permeate in the solution to be filtered is recycled, and wherein, before the start of utilization of the membrane, the permeate and the retentate are circulated through the nanofiltration membrane for a set time. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     Other characteristics will appear on reading the description that follows, making reference to the drawing wherein: 
     FIG. 1 shows a device which enables the use of a nanofiltration module according to the present invention. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In the following description, the method of the invention to improve the functioning of a membrane of a nanofiltration device will be described in a nanofiltration device utilized to treat a photographic bath. But clearly the method of the invention can be used in any nanofiltration system for treating any type of effluent, in particular effluents having a relatively high saline concentration. 
     With reference to FIG. 1, a device can be seen for using a nanofiltration device. The device comprises a tank  10  in which is found the solution to be filtered and recycled. The device also comprises a nanofiltration module  20  comprising a membrane  21  through which the solution to be treated is circulated. The solution circulates in a set of pipes  30 . The tank  10  is fed with solution by a first pipe  31  coming from the treatment bath. A second pipe  32  enables the solution contained in the tank  10  to be taken to the nanofiltration module  20 . A pump  40  enables the solution to be moved in this pipe and the flow rate of the solution to be regulated through the nanofiltration module. A third pipe  33  is provided to take the retentate into the tank  10 . A fourth pipe  34  is provided to clear the permeate from the device so as to recycle it in the treatment bath (not shown). This pipe  34  is used in production mode, i.e. when the solution contained in the tank  10  is treated. 
     Further the device comprises a fifth pipe  35  in which the permeate is taken to the tank  10 . This pipe  35  is only used when the device is in initialization mode, i.e. in a configuration used before the production mode after membrane balancing. A three-way valve  50  enables switching between the two use modes, i.e. the initialization mode and the production mode. 
     During the treatment of a solution, a specified amount of solution to be filtered and recycled, coming from a photographic treatment bath, is collected in the tank  10 . For a set time, e.g. for several minutes, the nanofiltration device is used in initialization mode until the membrane  21  is ionically balanced. The initialization phase lasts between 1 and 10 minutes, preferably between 2 and 5 minutes. The solution present in the tank  10  is pumped using pump  40 . The nanofiltration module  20  is fed in this way. The membrane  21  enables separation of the retentate and the permeate which are sent back into the tank  10  through the pipes  33  and  35  respectively. In this way the membrane  21  is balanced and its separation quality is increased so as to obtain a permeate that is the most purified possible. After having used the device in an initialization mode, it can be used in production mode. Therefore, the permeate is cleared from the device by the pipe  34  and recycled into the photographic treatment bath. 
     Preferably, at the end of use in production mode, the nanofiltration device is rinsed with a relatively small volume of rinsing solution. The rinsing solution is, for example, mains water, distilled water, or even permeate. Preferably, the device is rinsed with a volume approximately equal to three to ten times the dead volume of the device, the dead volume being the volume liable to be contained in the device outside the tank  10 , i.e. in the nanofiltration module  20 , the pipes  30 , and the pump  40 . 
     The invention is described in detail in the following example. 
     EXAMPLE 
     In this example, the nanofiltration device is utilized to treat a photographic bath. 
     Washing water coming from a seasoned stabilization bath is collected in the tank  10  through pipe  31 . When the tank is full, the pump is run and the two modes previously described are operated. 
     In this way 10 liters of stabilization bath are filtered with a nanofiltration module equipped with an NF45 FILMTEC® membrane with useful area 2.21 m 2 . The feed rate of the nanofiltration module is 600 l/h with a mean pressure of 30 bar. 
     The bath comprises: 
     Thiosulfate: 13,308 mg/l 
     Sulfate: 9,921 mg/l 
     Silver: 920 mg/l 
     Iron: 2,650 mg/l 
     COD (Chemical Oxygen Demand): 33,440 mg/l 
     TOC (Total Organic Carbon): 8,100 mg/l 
     The permeate was sampled at various outputs of recycled water, the output being defined thus:        R   =       permeatevolume     initial                 volume                 of                 solution                 to                 be                 treated       ×   100                            
     Table I groups together the analysis of the concentration of the various chemical compounds contained in the permeate for a permeate output of 70%. The first column shows the concentration of the chemical compounds present in the permeate when the nanofiltration device is used directly in production mode, without initialization phase. The second column shows the concentration of the chemical compounds present in the permeate when the nanofiltration device is used with an initialization phase before the production mode according to the invention. In this second case, the initialization phase lasts about five minutes. In both cases, the concentration of the contaminating chemical compounds in a tank is measured in which the permeate coming from the pipe  34  is recovered when the volume of permeate collected is 70% of the initial volume to be treated. 
     
       
         
               
               
             
               
               
               
             
               
               
               
             
           
               
                   
                 TABLE I 
               
             
             
               
                   
                   
               
               
                   
                 Concentration (mg/l) in the permeate 
               
             
          
           
               
                   
                 Without initialization 
                 With initialization phase 
               
               
                 Chemical compound 
                 phase 
                 (invention) 
               
               
                   
               
             
          
           
               
                 Thiosulfate 
                 1,536 
                 820 
               
               
                 Sulfate 
                 674 
                 435 
               
               
                 Silver 
                 44 
                 22 
               
               
                 Iron 
                 35 
                 6.3 
               
               
                 COD 
                 8,170 
                 5,840 
               
               
                 TOC 
                 2,260 
                 1,650 
               
               
                   
               
             
          
         
       
     
     Table II groups together the analysis of the concentration of the various chemical compounds contained in the permeate for a permeate output of 90%. The first column shows the concentration of the chemical compounds present in the permeate when the nanofiltration device is used directly in production mode, without initialization phase. The concentration is then measured. The second column shows the concentration of the chemical compounds present in the permeate when the nanofiltration device is used with an initialization phase before the production mode according to the invention. In this second case, the initialization phase lasts about five minutes. In both cases, the concentration of the contaminating chemical compounds in a tank is measured in which the permeate coming from the pipe  34  is recovered when the volume of permeate collected is 90% of the initial volume to be treated. 
     
       
         
               
               
             
               
               
               
             
               
               
               
             
           
               
                   
                 TABLE II 
               
             
             
               
                   
                   
               
               
                   
                 Concentration (mg/l) in the permeate 
               
             
          
           
               
                   
                 Without initialization 
                 With initialization phase 
               
               
                 Chemical compound 
                 phase 
                 (invention) 
               
               
                   
               
             
          
           
               
                 Thiosulfate 
                 3,739 
                 1,923 
               
               
                 Sulfate 
                 1,272 
                 678 
               
               
                 Silver 
                 115 
                 51 
               
               
                 Iron 
                 60 
                 15 
               
               
                 COD 
                 9,100 
                 8,110 
               
               
                 TOC 
                 2,425 
                 2,190 
               
               
                   
               
             
          
         
       
     
     These examples show that when an initialization phase is used in the nanofiltration process, the concentration of filtered chemical compounds that are found in the permeate decreases significantly. In this way the functioning of the nanofiltration membrane is improved. 
     The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.