Abstract:
A method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, the liquid suspension being applied to the outer surface of the porous hollow membrane to induce and sustain filtration through the membrane walls. The method of cleaning comprises the steps of applying a cleaning solution to one side of the membrane wall; applying a pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the one side of the membrane wall to the other side of the membrane wall and applying a reverse pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the other side of the membrane wall back to the one side of the membrane wall.

Description:
RELATED APPLICATIONS 
       [0001]    This application claims the benefit under 35 U.S.C. §121 as a division of U.S. application Ser. No. 11/722,411, titled “CLEANING IN MEMBRANE FILTRATION SYSTEMS,” filed on Jun. 21, 2007, as a national stage application under 35 U.S.C. §371 of PCT Application Serial No. PCT/AU05/01919 titled “CLEANING IN MEMBRANE FILTRATION SYSTEMS,” filed on Dec. 19, 2005, which claims priority to AU Provisional Application Serial No. 2004907391 titled “CLEANING IN MEMBRANE FILTRATION SYSTEMS,” filed Dec. 24, 2004, each of which are herein incorporated by reference in their entireties. 
     
    
     BACKGROUND 
       [0002]    1. Field of Invention 
         [0003]    The present invention relates to the backwashing of hollow permeable membranes used in membrane filtration systems and, in particular, to an improved method of backwashing and cleaning the hollow permeable membranes. 
         [0004]    2. Background Art 
         [0005]    Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. 
         [0006]    Known backwash systems include those described in our earlier International Application No. WO93/02779 the subject matter of which is incorporated herein by cross-reference. 
         [0007]    During cleaning of membranes, cleaning solutions are often flowed through the membranes and their permeable walls to clean foulants from the membranes. Applying the cleaning solution under pressure assists the removal of foulants from the surface. 
         [0008]    The typical known cleaning procedure for membranes involves cleaning the membranes in-situ. This procedure adds a set concentration of chemical, commonly 2% citric acid followed by 200-1,000 ppm sodium hypochlorite, to the membrane in a solution of filtrate. This usually occurs at the start of the two hour cleaning period, after which the cleaning solution is filtered through the membrane and left to soak. 
         [0009]    As the nature of membrane fouling varies according to feed quality and type, flux through the membrane and hours of operation, the amount and length of chemical cleaning required in each situation also varies. This often results in a one process fits all approach where a standard chemical cleaning stage is applied regardless of the amount of fouling. This can lead to large amounts of cleaning solution being used unnecessarily with the effect of additional cost and environmental impact in disposing of the waste solution after cleaning is complete. 
       SUMMARY 
       [0010]    It is an object of the invention to overcome or at least ameliorate one or more of the disadvantages of the prior art or at least provide a useful alternative. 
         [0011]    According to a first aspect, the present invention provides a method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, the liquid suspension being applied to the outer surface of the porous hollow membranes to induce and sustain filtration through the membrane walls wherein: 
         [0012]    (a) some of the liquid suspension passes through the walls of the membranes to be drawn off as clarified liquid or permeate from the hollow membrane lumens, and 
         [0013]    (b) at least some of the solids are retained on or in the hollow membranes or otherwise as suspended solids within the liquid surrounding the membranes, the method of cleaning comprising the steps of:
       i) removing, at least partially, liquid from the filtrate side of the membrane;   ii) removing, at least partially, liquid from the outer side of the membrane;   iii) applying a cleaning solution to the outer side of the membrane;   iv) applying a pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the outer side of the membrane into the membrane lumen to at least partially fill the lumen with cleaning solution;   v) isolating the outer side of the membrane;   vi) applying a pressurized gas to the filtrate side of the membrane wall to cause flow of the cleaning solution back to the outer side through the membrane wall;   vii) accumulating the increased pressure developed on the outer side of the membrane as a result of said flow of cleaning solution; and   viii) releasing the pressure applied by the pressurized gas to the filtrate side of the membrane wall to cause flow of the cleaning solution through the membrane from the outer side to the filtrate side under the effect of the accumulated pressure on the outer side of the membrane wall.       
 
         [0022]    For preference the cleaning solution is a chemical cleaning solution. 
         [0023]    Preferably, in step vi) gas, usually air, is applied such that the membrane lumen is substantially drained of cleaning solution. Preferably the pressure is accumulated in step vii) in a gas space provided on the outer side of the membrane wall or alternatively in a bladder arrangement. 
         [0024]    The differential pressure of step iv) may be provided by applying gas pressure to the outer side of the membrane wall or by applying a vacuum to the filtrate side. 
         [0025]    According to a further aspect the present invention provides a method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, the liquid suspension being applied to the outer surface of the porous hollow membranes to induce and sustain filtration through the membrane walls wherein: 
         [0026]    (a) some of the liquid suspension passes through the walls of the membranes to be drawn off as clarified liquid or permeate from the hollow membrane lumens, and 
         [0027]    (b) at least some of the solids are retained on or in the hollow membranes or otherwise as suspended solids within the liquid surrounding the membranes, the method of cleaning comprising the steps of:
       i) applying a cleaning solution to one side of the membrane wall;   ii) applying a pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the one side of the membrane wall to the other side of the membrane wall; and   iii) applying a reverse pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the other side of the membrane wall back to the one side of the membrane wall.       
 
         [0031]    According to yet a further aspect the present invention provides a method of cleaning permeable, hollow membranes in an arrangement of the type wherein a pressure differential is applied across the walls of the permeable, hollow membranes immersed in a liquid suspension, said liquid suspension being applied to the outer surface of the porous hollow membranes to induce and sustain filtration through the membrane walls wherein: 
         [0032]    (a) some of the liquid suspension passes through the walls of the membranes to be drawn off as clarified liquid or permeate from the hollow membrane lumens, and 
         [0033]    (b) at least some of the solids are retained on or in the hollow membranes or otherwise as suspended solids within the liquid surrounding the membranes, the method of cleaning comprising the steps of:
       i) removing, at least partially, liquid from the filtrate side of the membrane;   ii) removing, at least partially, liquid from the outer side of the membrane;   iii) applying a cleaning solution to the outer side of the membrane;   iv) applying a pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the outer side of the membrane into the membrane lumen to at least partially fill the lumen with cleaning solution; and   v) applying a pressure differential across the membrane wall to cause flow of the cleaning solution through the wall from the lumen side of the membrane back to the outer side of the membrane lumen.       
 
         [0039]    Preferably the pressure differential in step v) is produced by applying a pressurized gas to the filtrate side of the membrane wall to cause flow of the cleaning solution back to the outer side through the membrane wall. 
         [0040]    The cleaning process can be repeated in cycles such that the cleaning solution is alternately moved from one side of the membrane to the other through the membrane wall. 
         [0041]    The process can be applied to membranes submerged in an open vessel as well as pressurized membrane filtration systems. 
         [0042]    According to another aspect of the present invention there is provided a method of controlling a chemical clean of a membrane comprising: 
         [0043]    measuring pH and/or membrane resistance of a membrane for at least a portion of said clean; and 
         [0044]    ceasing said chemical clean when pH and/or membrane resistance attains a predetermined value. 
         [0045]    According to another aspect of the present invention there is provided a method of controlling a chemical clean of a membrane comprising: 
         [0046]    measuring the pH and/or membrane resistance of a membrane for at least a portion of the clean; 
         [0047]    measuring an elapsed time of the clean; 
         [0048]    calculating a rate of change of pH with respect to time (dpH/dt) and/or a rate of change of membrane resistance (dR/dt) with respect to time; and 
         [0049]    ceasing the chemical clean when dpH/dt and/or dR/dt attains a predetermined value. 
         [0050]    According to another aspect of the present invention there is provided a method of controlling the chemical cleaning of a filtration system comprising the steps of: 
         [0051]    measuring the membrane resistance of a membrane for at least a portion of the clean; 
         [0052]    measuring an elapsed time of the clean; 
         [0053]    calculating a rate of change of membrane resistance (dR/dt) with respect to time; and 
         [0054]    using dR/dt to calculate a duration for completion of the clean. 
         [0055]    According to another aspect of the present invention there is provided a method of controlling a chemical clean of a membrane comprising: 
         [0056]    increasing the amount of chemical cleaning agent present during the clean; 
         [0057]    measuring the membrane resistance of a membrane for at least a portion of the clean; and 
         [0058]    ceasing the increase in chemical cleaning agent when the membrane resistance attains a predetermined value. 
         [0059]    Preferably, the amount of cleaning agent is increased incrementally. 
         [0060]    For preference, the predetermined value approximates a steady-state value of membrane resistance. Preferably, the membranes are microfiltration or ultrafiltration type membranes. 
     
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         [0061]    The accompanying drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings: 
           [0062]      FIG. 1   a  shows a simplified sectional side elevation of a membrane module with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens; 
           [0063]      FIG. 1   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 1   a;    
           [0064]      FIG. 1   c  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 1   a;    
           [0065]      FIG. 2   a  shows a simplified sectional side elevation of a membrane module of  FIG. 1  with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens; 
           [0066]      FIG. 2   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 2   a;    
           [0067]      FIG. 3   a  shows a simplified sectional side elevation of a membrane module of  FIG. 1  with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens; 
           [0068]      FIG. 3   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 3   a;    
           [0069]      FIG. 3   c  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 3   a;    
           [0070]      FIG. 4   a  shows a simplified sectional side elevation of another embodiment of a membrane module with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens; 
           [0071]      FIG. 4   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 4   a;    
           [0072]      FIG. 4   c  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 4   a;    
           [0073]      FIG. 5   a  shows a simplified sectional side elevation of the membrane module of  FIG. 4  with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens; 
           [0074]      FIG. 5   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 5   a;    
           [0075]      FIG. 6   a  shows a simplified sectional side elevation of another embodiment of a membrane module with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens; 
           [0076]      FIG. 6   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 6   a;    
           [0077]      FIG. 6   c  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 6   a;    
           [0078]      FIG. 7   a  shows a simplified sectional side elevation of the membrane module of  FIG. 6  with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens; 
           [0079]      FIG. 7   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 7   a;    
           [0080]      FIG. 8   a  shows a simplified sectional side elevation of an embodiment of a membrane module in an open vessel with a lower portion of the module immersed in a chemical cleaning solution and suction applied to the membrane lumens; 
           [0081]      FIG. 8   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 8   a;    
           [0082]      FIG. 8   c  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 8   a;    
           [0083]      FIG. 9   a  shows a simplified sectional side elevation of a membrane module of the embodiment of  FIG. 8  with a lower portion of the module immersed in a chemical cleaning solution and pressurized gas applied to the membrane lumens; 
           [0084]      FIG. 9   b  shows an enlarged sectional view of the membranes in the indicated region of  FIG. 9   a;    
           [0085]      FIG. 10  shows a graph of transmembrane pressure (TMP) measured over time for a membrane module of the type illustrated in  FIGS. 8 and 9  undergoing a chemical clean using the method according to the invention; 
           [0086]      FIG. 11  shows a graph of membrane resistance measured over time for two types of chemical cleaning process with incremental increases in the volume of chemical cleaning agent added during the cleaning process; and 
           [0087]      FIG. 12  shows a graph of membrane resistance measured over time with incremental increases in the volume of chemical cleaning agent added during the cleaning process. 
       
    
    
     DETAILED DESCRIPTION 
       [0088]    This invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” “having,” “containing,” “involving,” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. 
         [0089]    Referring to the  FIGS. 1 to 7 , there is shown a membrane module  5  having a plurality of hollow fiber membranes  6 . The fiber membranes  6  have their lumens  7  closed at the lower end in a lower pot  8  and open at the upper end through upper pot  9 . The module  5  is contained in a vessel  10  having a controllable valve  11  for opening/closing the vessel  10  to atmosphere. Upper pot  8  is connected to a filtrate collection chamber  12  having a port  13 . 
         [0090]    One embodiment of the cleaning process according to the invention will now be described with reference to  FIGS. 1 to 3 . As best shown in  FIGS. 1   a  to  1   c , liquid remaining in lumens  7  after filtration is drained while liquid remaining in the vessel  10  is also at least partially drained. The vessel  10  is then, at least partially, filled with cleaning solution  14  as best shown in  FIG. 1   a . A differential pressure is then applied across the membrane walls  15 , in this embodiment by applying a vacuum to port  13 , so that the cleaning solution  14  is drawn through the membrane walls  15  (as shown in  FIG. 1   b ) and up the membrane lumen  7  until it is, at least partially, filled with cleaning solution. 
         [0091]    As shown in  FIGS. 2   a  and  2   b , the valve  11  is then closed to isolate the vessel  10  while pressurized gas is applied through port  13  to the cleaning solution filling the membrane lumen  7  and displaced through the membrane wall  15  until the lumen  7  is substantially drained of cleaning solution. With the vessel  10  isolated, the transfer of cleaning solution  14  through the membrane wall  15  to the outer side of the membrane  6  results in the pressure within the vessel to increase as the gas space  16  within the vessel  10  is compressed. 
         [0092]    As shown in  FIGS. 3   a  to  3   c , the lumen side of the membranes are vented to atmosphere. The accumulated pressure in the gas space  16  then forces the cleaning solution  14  to flow back through the membrane wall  15  as best shown in  FIG. 3   b.    
         [0093]      FIGS. 4   a  to  7   b  illustrate embodiments of the invention where a bladder arrangement may be used instead of the gas space  16  to accumulate pressure. 
         [0094]    Referring to  FIGS. 4   a  to  4   c , the operation is similar to that shown in  FIGS. 3   a  to  3   c , however, in this embodiment when the lumen side of the membranes is vented to atmosphere through valve  17 , the bladder  16  delivers pressure to the feed side of the vessel  10  forcing the cleaning solution  14  through the membrane wall  15  and along the membrane lumen  7  as best shown in  FIGS. 4   b  and  4   c.    
         [0095]    Referring to  FIGS. 5   a  and  5   b , the pressurizing of the lumen/filtrate side is shown. Pressurized gas is applied to the lumen/filtrate side of the membranes  6  by feeding pressurized gas through line  18  and valve  17  to port  13 . The pressurized gas causes the cleaning solution within the lumen  7  to flow through the membrane wall  15  to the outer side of the membrane resulting in the pressure within the vessel  10  increasing and being transferred to the bladder  16  connected to the vessel  10  through line  19  and valve  11 . 
         [0096]      FIGS. 6   a  to  6   c  show a similar arrangement to  FIGS. 4   a  to  4   c  but in this embodiment the gas pressure is applied to the vessel  10  from an external source, rather than the bladder  16 , through line  19  and valve  11 . Bladder  16  is used to accumulate pressure on the lumen side of the membranes  6  as shown in  FIG. 6   a.    
         [0097]    As shown in  FIGS. 7   a  and  7   b , when the reverse flow of cleaning solution is required, the vessel  10  is vented to atmosphere through line  19  and valve  11  and bladder  16  releases accumulated pressure to the lumen side forcing the cleaning solution  14  within the lumens back through the lumen walls  15  (see  FIG. 7   b ). 
         [0098]    Referring to  FIGS. 8 and 9 , an embodiment of the cleaning process according to the invention is illustrated where the vessel  10  is open to atmosphere. In this embodiment flow of cleaning solution through the membrane wall  15  is provided by alternately applying suction/vacuum or pressure to the lumen side of the membranes  6 . The membrane module  5  is again immersed at least partially in chemical cleaning solution  14  and suction is applied to the open ends of the fiber membrane lumens  7 . As best shown in  FIG. 8   b , the cleaning solution  14  is drawn through the membrane wall  15  and into the fiber membrane lumen  7 . The cleaning solution  14  is then drawn up through the lumen  7  until it is completely filled as shown in  FIG. 8   c . As shown in  FIGS. 9   a  and  9   b , pressurized gas is then applied to the cleaning solution  14  filling the membrane lumen  7  and the cleaning solution is displaced through the membrane wall  15  as previously described. 
         [0099]    The process illustrated in the embodiments can be repeated in cycles such that cleaning solution is alternatively moved from one side of the membrane wall  15  to the other. This flow of cleaning solution to and from the membrane lumens  7  and well as along their length results in an effective chemical clean of the membrane module  5 . 
         [0100]      FIG. 10  shows the results of applying the cleaning regime according to the invention to a membrane module of the type where the vessel  10  is open to atmosphere. The cleaning process was performed as follows: 
         [0101]    1. The membrane vessel was filled with filtrate via backfilling from the lumen side to the shell side, with simultaneous chlorine dosing into the filtrate line. The vessel filtrate level was about 30%, with a target volume of cleaning solution (NaOCl) of 30 mL. 
         [0102]    2. The filtrate was then recirculated briefly through the system in order to ensure a well-mixed cleaning solution. 
         [0103]    3. The lumens were then drained of liquid by 100 kPa air being applied to the filtrate line. This allowed the cleaning solution to diffuse through the pores and down the fiber length, which raised the filtrate vessel level. This step may be ended when the liquid level stops rising. 
         [0104]    4. The lumens were then filled with the cleaning solution by using vacuum air applied to the lumen side of the membranes. During this step the level in the filtrate tank dropped as the liquid was pulled into the fiber lumens. This step may be ended when the liquid level stops falling. 
         [0105]    5. The lumen fill and drain steps were repeated until contact time had reached 1,800 seconds. 
         [0106]    6. After 1,800 seconds of cleaning solution contact, the vessel was topped up with feed. This allowed the remaining free chlorine in the cleaning solution to contact with the part of the module that was exposed during the clean. 
         [0107]    7. The system was then aerated to maximize contact of solution with module. 
         [0108]    8. The tank was then drained and flushed with filtrate before returning to service. 
         [0109]    The data graphed in  FIG. 10  shows a period when the cleaning regime was performed once every 24 filtration hours for 4 days in succession, with the module operating at 1.7 m 3 /hr with a 30 minute backwash interval. Chlorine in the form of sodium hypochlorite (NaOCl) was used, the average free chlorine concentration during the clean being 100 ppm. Feed water turbidity was between 60-90 NTU throughout. 
         [0110]    The data shown in  FIG. 10  illustrates the regular reduction in transmembrane pressure (TMP) flowing each clean. 
         [0111]    One embodiment of the invention seeks to minimize the amount of chemical required by adding it incrementally to the membrane tank, whilst monitoring resistance through the membrane during a recirculation stage in the cleaning process. Chemical additions can cease when the further addition of chemical leads to change in the membrane resistance below a predetermined level, hence minimizing the amount of excess chemical agent used in the cleaning process. 
         [0112]    The resistance value can be monitored during filtrate recirculation. Typically, during a standard cleaning procedure, the chemical cleaning solution is recirculated at the start of the clean only, followed by up to 48 hours of soaking of the membranes. In the present embodiment, the chemical cleaning solution is recirculated for several minutes (for example—3 minutes) every 15-30 minutes during the soak/aeration steps, allowing the membrane resistance to be measured periodically throughout the cleaning process. 
         [0113]    When the change in resistance per 3 recirculations drops below a predetermined value (for example—0.1) the cleaning process has recovered the maximum performance at that chemical concentration and further chemical agent is added. When the addition of further chemical agent effects the change in resistance by less than the predetermined value per 3 recirculations (for example—0.1), no further recovery can be achieved and the cleaning process can therefore be terminated immediately. Conversely, the cleaning potential can be maximized by extending the cleaning process so that the change in resistance per 3 circulations is below a certain predetermined value.  FIG. 11  shows a graph of resistance value variation of the duration of the cleaning process for two different cleaning regimes using citric (CIP1) and chlorine (CIP2) cleaning agents. 
         [0114]    Referring to the graph shown in  FIG. 12 , the volume of chemical agent begins around 100 ml as shown at A resulted in a significant drop in membrane resistance. The amount of chemical agent was further increased as shown at B and C resulting in further decreases in membrane resistance. Once the volume of chemical agent reached about 250 ml, the membrane resistance change reached substantially a steady state as shown at D and further increases (E) in chemical agent had minimal effect. At this stage the volume of chemical agent added can be ceased without adversely affecting the cleaning process and recovery in transmembrane flow. 
         [0115]    It will be appreciated that using the above measurements it is possible to determine a resistance profile during the cleaning process for a particular membrane arrangement or configuration. The resistance profile can then be used to predict the end of cleaning process time, half-life, and reduce chemical use in simultaneous cleans of similar systems. The resistance profile may be further used to determine whether chemicals are required to be added during the cleaning process with the type and amount of chemical being dependent on feed and foulant quality. 
         [0116]    Typical cleaning solutions which may be used include acids, caustic solutions and oxidizing solutions (e.g. chlorine). 
         [0117]    The invention may be embodied in a similar apparatus to that described in the aforementioned International Application No. WO93/02779 appropriately modified to operate in accordance with the inventive method. 
         [0118]    It will be appreciated that further embodiments and exemplifications of the invention are possible without departing from the spirit or scope of the invention described. 
         [0119]    Having thus described several aspects of at least one embodiment of this invention, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the spirit and scope of the invention. Accordingly, the foregoing description and drawings are by way of example only.